Azole derivatives and agricultural and horticultural chemical composition containing the same

ABSTRACT

Disclosed herein are an azole derivative represented by the formula(I): ##STR1## wherein R 1  and R 2  respectively represent a (C 1  -C 5 ) alkyl group or a hydrogen atom; X represents a halogen atom, a (C 1  -C 5 ) alkyl group or a phenyl group; n represents an integer of from 0 to 2 and A represents a nitrogen atom or a CH, provided that R 1  is not a hydrogen atom when R 2  is a hydrogen atom, a process for producing the azole derivative represented by the formula(I), and an agricultural and horticultural composition containing the azole derivative represented by the formula(I).

BACKGROUND OF THE INVENTION

The present invention relates to an azole derivative having a plantdiseases controlling activity and plant growth regulating activity, aprocess for producing the azole derivative and an agricultural andhorticultural composition containing the azole derivative as an activeingredient. More in detail, the present invention relates

(1) an azole derivative represented by the formula (I): ##STR2## whereinR¹ and R² respectively represent a(C₁ -C₅)alkyl group or a hydrogenatom; X represents a halogen atom, a(C₁ -C₅)alkyl group or a phenylgroup; n represents an integer of from 0 to 2 and A represents anitrogen atom or a CH, provided that R¹ is not a hydrogen atom when R²is a hydrogen atom,

(2) a process for producing the azole derivative represented by theformula (I), which process comprises steps of

(a) (i) reacting an alkyl ester of 2-oxocyclopentanecarboxylic acid witha substituted benzyl halide and reacting the thus obtained alkyl esterof 1-(substituted benzyl)-2-oxocyclopentanecarboxylic acid with a(C₁-C₅)alkyl halide, (ii) reacting an alkyl ester of 3-(C₁ -C₅alkyl)-2-oxocyclopentanecarboxylic acid with a substituted benzylhalide, or (iii) reacting 1-(substituted benzyl)-3-(C₁ -C₅alkyl)-2-oxocyclopentanecarboxylic acid with a (C₁ -C₅)alkyl halide,thereby obtaining an ester derivative of cyclopentanecarboxylic acidrepresented by the formula (V): ##STR3## wherein R¹ and R² respectivelyrepresent a (C₁ -C₅)alkyl group or a hydrogen atom; R represents a (C₁-C₅)alkyl group; X represents a halogen atom, a(C₁ -C₅)alkyl group or aphenyl group and n represents an integer of from 0 to 2, provided thatR¹ is not a hydrogen atom when R² is a hydrogen atom,

(b) subjecting the thus obtained ester derivative ofcyclopentanecarboxylic acid to hydrolytic decarboxylation, therebyobtaining a cyclopentanone derivative represented by the formula (IV):##STR4## wherein R¹, R², X and n respectively represent the same definedas above,

(c) subjecting the thus obtained cyclopentanone derivative to an oxiranereaction while using sulfonium ylide or oxosulfonium ylide or subjectinga methylenecyclopentane derivative obtained from the thus obtainedcyclopentanone derivative by Wittig reaction and represented by theformula (III): ##STR5## wherein R¹, R², X and n respectively representthe same defined as above, into epoxidation, thereby converting thecyclopentanone derivative into an oxirane derivative represented by theformula (II): ##STR6## wherein R¹, R², X and n respectively representthe same defined as above, and then

(d) reacting the thus obtained oxirane derivative with an 1,2,4-triazoleor an imidazole represented by the formula (VI): ##STR7## wherein Mrepresents a hydrogen atom or an alkali metal atom and A represents anitrogen atom or a --CH═, thereby obtaining the azole derivativerepresented by the formula (I): ##STR8## wherein R¹ and R² respectivelyrepresent a(C₁ -C₅)alkyl group or a hydrogen atom; X represents ahalogen atom, a(C₁ -C₅)alkyl group or a phenyl group; n represents aninteger of from 0 to 2 and A represents a nitrogen atom or a CH,provided that R¹ is not a hydrogen atom when R² is a hydrogen atom, and

(3) an agricultural and horticultural composition having a fungicidalactivity and a plant growth regulating activity, which comprises aneffective amount of the azole derivative represented by the formula (I).

The damage of the crops due to various plant diseases is enormous, andalso, a problem due to the environmental pollution by the chemicals forcontrolling these plant diseases has arisen

Accordingly, an offer of an agricultural and horticultural chemicalwhich has a controlling effect against the plant diseases, is low intoxicity to men, beasts, birds and fishes and is low in phytotoxicity touseful plants, that is, an agricultural and horticultural chemical whichis high in safety on handling, small in influence to the environment andhas an excellent controlling effect against plant diseases in a broadrange has been demanded.

In order to fulfill such a demand, the following agricultural andhorticultural fungicides have hitherto been proposed.

(1) Compounds of triazoles or imidazoles represented by the followingformula: ##STR9## wherein R¹ represents a --CH═CH--X, a --C.tbd.C--X ora --CH₂ --CH₂ --X (wherein X is a hydrogen atom, an alkyl group, ahydroxyalkyl group, an alkoxyalkyl group, a cycloalkyl group, asubstituted aryl group which may be substituted, an aralkyl group whichmay be substituted, an aryloxyalkyl group which may be substituted or aheterocyclic group which may be substituted); R² represents an alkylgroup, a cycloalkyl group or an aryl group which may be substituted; Zrepresents a chlorine atom, a cyano group or a --OR³ (wherein R³ is ahydrogen atom, an acetyl group, an alkyl group, an alkenyl group or anaralkyl group) and Y represents a nitrogen atom or a CH, an acidaddition salt thereof and a metal complex thereof [refer to JapanesePatent Application Laid-Open(KOKAI) No. 57-114577 (1982) correspondingto U.S. Pat. No. 4,507,140 and European Patent No. 52424.].

(2) Compounds of triazoles or imidazoles represented by the followingformula: ##STR10## wherein R represents a cross-linking group:--(CH₂)_(n) -(wherein n is 0, 1 or 2), a cross-linking group: a--CH═CH--, an --O--, an --S--, an --NH-- or a --C(═O)--; X represents anitrogen atom or a CH; Y and Z may be the same or different from eachother and respectively represents a halogen atom, an alkyl group, analkoxy group, a haloalkoxy group, a haloalkyl group, a nitro group, aphenyl group or a phenoxy group, and m and p respectively represent 0,1,2 or 3, an acid thereof, a metal complex thereof and functionalderivatives thereof [refer to Japanese Patent Application Laid Open No.57-126479(1982) corresponding to European Patent No. 52425].

(3) Derivatives of 1-hydroxyethylazole, represented by the followingformula: ##STR11## wherein R represents an alkyl group, a cycloalkylgroup which may be substituted or a phenyl group which may besubstituted, X represents a nitrogen atom or a CH; Y represents a --OCH₂--, a --CH₂ --CH₂ -- or a --CH═CH--; Z represents a halogen atom, analkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, ahalogenoalkyl group, a halogenoalkoxy group, a halogenoalkylthio group,phenyl group which may be substituted, a phenoxy group which may besubstituted or phenylalkyl group which may be substituted or aphenylalkoxy group which may be substituted and m represents 0, 1, 2 or3, an acid addition salt thereof and a metal complex thereof [refer toJapanese Patent Application Laid-Open (KOKAI) No. 57-16868 (1982)corresponding to U.S. Pat. No. 4,532,341 and European Patent No. 40345].

(4) Cycloaliphatic alcoholic compounds represented by the followingformula: ##STR12## wherein R⁶ represents an unsubstituted phenyl groupor a phenyl group substituted by from 1 to 5 groups selected from thegroup consisting of halogen atom(s), amino group(s), nitro group(s),cyano group(s), phenyl group(s), halogenophenyl group(s), (C₁ -C₁₀)alkylgroup(s), halogeno(C₁ -C₁₀)alkyl group(s), (C₁ -C₁₀)alkoxy group(s),halogeno(C₁ -C₁₀)alkoxy group(s), (C₁ -C₁₀)alkylthio group(s), (C₁-C₁₀)alkylenedioxy group(s), (C₁ -C₁₀)alkylamino group(s) and di(C₁-C₁₀)alkylamino groups; X represents a nitrogen atom or a methine group;a ring A is a cyclopentane ring, a cyclohexane ring, a cycloheptanering, an indane ring, a tetrahydronaphthalene ring or abenzocyclopeptane ring, each of the respective rings not having beensubstituted or having been substituted in the benzene ring thereof byfrom one to four of the above-mentioned substituents [refer to JapanesePatent Application Laid-Open (KOKAI) No. 58-189171 (1983) correspondingto U.S. Pat. No. 4,503,062 and European Patent No. 94146].

(5) Triazole compounds or imidazole compounds represented by thefollowing formula: ##STR13## wherein W is a CH or a nitrogen atom; Q isa substituted or unsubstituted aryl group, particularly a substituted orunsubstituted phenyl group, a substituted or unsubstituted aralkyl, or asubstituted or unsubstituted alkyl group; R¹, R², R³, R⁴, R⁵, R⁶, R⁷ andR⁸ may be the same or different from each other and respectivelyrepresent a hydrogen atom, a hydroxy group, an alkyl group, a cycloalkylgroup, a substituted or unsubstituted aralkyl group, a substituted orunsubstituted phenyl group, or any of the pairs of R¹ and R², R³ and R⁴, R⁵ and R⁶ or R⁷ and R⁸ represents a carbonyl group (C═O) together withthe adjacent ring-carbon atom; R⁹ and R¹⁰ may be the same or differentfrom each other and represent respectively a hydrogen atom, an alkylgroup, a cycloalkyl group, a substituted or unsubstituted aralkyl groupor a substituted or unsubstituted phenyl group and n is 0 or 1, astereoisomer thereof, an acid addition salt thereof and a metal complexthereof [refer to Japanese Patent Application Laid-Open (KOKAI) No.60-215674 (1985) corresponding to European Patent No. 153797].

As a result of the studies of some of the present inventors forproviding an agricultural and horticultural fungicide which is high insafety on handling, is small in influence to the environment and showsan excellent controlling effect against the plant diseases of a broadrange, they have found an azole derivative represented by the followingformula: ##STR14## wherein X represent respectively a halogen atom, analkyl group, a haloalkyl group, a phenyl group, a cyano group or a nitrogroup; n represents an integer of from 0 to 5 and A represents anitrogen atom or a CH, provided that X may be the same or different fromeach other when n is 1 to 5 [refer to Japanese Patent ApplicationLaid-Open (KOKAI) No. 62-149667 (1987) corresponding to U.S. patentapplication Ser. No. 06/903,992].

The present inventors have further studied a synthesis of many azolederivatives and an examination on the utility thereof in order to obtainan agricultural and horticultural fungicide which is low in toxicity tomen and beasts, is high in safety on handling and shows an excellentcontrolling effect against plant diseases of a broad range, and as aresult it has been found that an azole derivative represented by theformula (I): ##STR15## R¹ and R² respectively represent a (C₁ -C₅)alkylgroup or a hydrogen atom; X represents a halogen atom, a(C₁ -C₅)alkylgroup or a phenyl group; n represents an integer of from 0 to 2 and Arepresents a nitrogen atom or a CH, provided that R¹ is not a hydrogenatom when R² is a hydrogen atom, not only has the afore-mentionedspecific properties but also can be effectively applied as a plantgrowth regulating agent, and on the basis of their finding, the presentinvention have been attained.

Namely, the object of the present invention is to provide with an azolederivative having the utility as the active ingredient of theagricultural and horticultural composition having a plant diseasescontrolling activity and a plant growth regulating activity, a processfor producing the azole derivative, and an agricultural andhorticultural composition which contains, as an active ingredient, theazole derivative which shows an excellent controlling effect on theplant diseases in a broad range and at the same time, shows a plantgrowth regulating effect, is low in toxicity and is excellent in safetyon handling.

SUMMARY OF THE INVENTION

In a first aspect of the present invention, there is provided an azolederivative represented by the formula (I): ##STR16## wherein R¹ and R²respectively represent a (C₁ -C₅)alkyl group or a hydrogen atom; Xrepresents a halogen atom, a (C₁ -C₅)alkyl group or a phenyl group; nrepresents an integer of from 0 to 2 and A represents a nitrogen atom ora CH, provided that R¹ is not a hydrogen atom when R² is a hydrogenatom.

In a second aspect of the present invention, there is provided a processfor producing an azole derivative represented by the formula (I):##STR17## wherein R¹ and R² respectively represent a (C₁ -C₅)alkyl groupor a hydrogen atom; X represents a halogen atom, a (C₁ -C₅)alkyl groupor a phenyl group; n represents an integer of from 0 to 2 and Arepresents a nitrogen atom or a CH, provided that R¹ is not a hydrogenatom when R² is a hydrogen atom, which process comprises the steps of

(a) (i) reacting an alkyl ester of 2-oxocyclopentanecarboxylic acid witha substituted benzyl halide and reacting the thus obtained alkyl esterof 1-(substituted benzyl)-2-oxocyclopentanecarboxylic acid with a (C₁-C₅)alkyl halide, (ii) reacting an alkyl ester of 3-(C₁ -C₅alkyl)-2-oxocyclopentanecarboxylic acid with a substituted benzyl halideor (iii) reacting 1-(substituted benzyl)-3-(C₁ -C₅alkyl)-2-oxocyclopentanecarboxylic acid with a (C₁ -C₅)alkyl halide,thereby obtaining an ester derivative of cyclopentanecarboxylic acidrepresented by the formula (V): ##STR18## wherein R¹ and R² respectivelyrepresent a (C₁ -C₅)alkyl group or a hydrogen atom; R represents a (C₁-C₅)alkyl group; X represents a halogen atom, a (C₁ -C₅)alkyl group or aphenyl group and n represents an integer of from 0 to 2, provided thatR¹ is not a hydrogen atom when R² is a hydrogen atom,

(b) subjecting the thus obtained ester derivative ofcyclopentanecarboxylic acid to hydrolytic decarboxylation, therebyobtaining a cyclopentanone derivative represented by the formula (IV):##STR19## wherein R¹, R², X and n respectively represent the samedefined as above,

(c) subjecting the thus obtained cyclopentanone derivative to an oxiranereaction while using sulfonium ylide or oxosulfonium ylide, orsubjecting a methylenecyclopentane derivative obtained from the thusobtained cyclopentanone derivative by Wittig reaction and represented bythe formula (III): ##STR20## wherein R¹, R², X and n respectivelyrepresent the same defined as above, to epoxidation, thereby convertingthe cyclopentanone derivative into an oxirane derivative represented bythe formula (II): ##STR21## wherein R¹, R², X and n respectivelyrepresent the same defined as above, and then

(d) reacting the thus obtained oxirane derivative with a 1,2,4-triazoleor an imidazole represented by the formula (VI): ##STR22## wherein Mrepresents a hydrogen atom or an alkali metal atom and A represents anitrogen atom or a CH.

In a third aspect of the present invention, there is provided anagricultural and horticultural composition having a fungicidal activityand a plant growth regulating activity, which comprises, as an activeingredient, an azole derivative represented by the formula (I):##STR23## wherein R¹ and R² respectively represent a (C₁ -C₅)alkyl groupor a hydrogen atom; X represents a halogen atom, a (C₁ -C₅)alkyl groupor a phenyl group; n represents an integer of from 0 to 2 and Arepresents a nitrogen atom or a CH, provided that R1 is not a hydrogenatom when R² is a hydrogen atom.

In a fourth aspect of the present invention, there is provided anoxirane derivative for producing an azole derivative represented by theformula (I), which is represented by the formula (II): ##STR24## whereinR¹ and R² respectively represent a (C₁ -C₅)alkyl group or a hydrogenatom; X represents a halogen atom, a (C₁ -C₅)alkyl group or a phenylgroup and n represents an integer of from 0 to 2, provided that R1 isnot a hydrogen atom when R² is a hydrogen atom.

In a fifth aspect of the present invention, there is provided amethylenecyclopentane derivative for producing an azole derivativerepresented by the formula (I), which is represented by the formula(III): ##STR25## wherein R¹ and R² respectively represent a (C₁-C₅)alkyl group or a hydrogen atom; X represents a halogen atom, a (C₁-C₅)alkyl group or a phenyl group and n represents an integer of from 0to 2, provided that R₁ is not a hydrogen atom when R² is a hydrogenatom.

In a sixth aspect of the present invention, there is provided acyclopentanone derivative for producing an azole derivative representedby the formula (I), which is represented by the formula (IV): ##STR26##wherein R¹ and R² respectively represent a (C₁ -C₅)alkyl group or ahydrogen atom; X represents a halogen atom, a (C₁ -C₅)alkyl group or aphenyl group and n represents an integer of from 0 to 2, provided thatR¹ is not a hydrogen atom when R² is a hydrogen atom.

In a seventh aspect of the present invention, there is provided an esterderivative of a cyclopentanecarboxylic acid for producing an azolederivative represented by the formula (I), which is represented by theformula (V): ##STR27## wherein R¹ and R² respectively represent a (C₁-C₅)alkyl group or a hydrogen atom; R represents a (C₁ -C₅)alkyl group;X represents a halogen atom, a (C₁ -C₅)alkyl group or a phenyl group andn represents an integer of from 0 to 2, provided that R¹ is not ahydrogen atom when R² is a hydrogen atom.

BRIEF EXPLANATION OF DRAWINGS

Of the attached drawings, FIGS. 1 to 76 show the infrared absorptionspectra of the azole derivatives according to the present inventionshown in Table 1. Namely, FIG. 1 shows the infrared absorption spectrumof the compound No. 1 in Table 1, FIG. 2 shows the infrared absorptionspectrum of the compound No. 2 in Table 1, FIG. 3 shows the infraredabsorption spectrum of the compound No. 3 in Table 1, and FIGS. 4 to 76show the respective infrared absorption spectra of the respectivecompounds Nos. 4 to 76 in Table 1.

The heart of the present invention lies in a novel azole derivativerepresented by the formula (I): ##STR28## wherein R¹ and R² respectivelyrepresent a (C₁ -C₅)alkyl group or a hydrogen atom; X represents ahalogen atom, a (C₁ -C₅)alkyl group or a phenyl group; n represents aninteger of from 0 to 2 and A represents a nitrogen atom or a CH,provided that R¹ is not a hydrogen atom when R² is a hydrogen atom, aprocess for producing the azole derivative represented by the formula(I), each of the compounds used as the intermediates, namely an oxiranederivative represented by the formula (II), a methylenecyclopentanederivative represented by the formula (III), a cyclopentanone derivativerepresented by the formula (IV) and an ester derivative ofcyclopentanecarboxylic acid represented by the formula (V), and anagricultural and horticultural composition containing the azolederivative represented by the formula (I) as an active ingredient andhaving fungicidal activity and plant growth regulating activity.

The physical and chemical properties of the azole derivative representedby the formula (I) and each of the intermediates for producing theabove-mentioned azole derivative are shown in Tables 1 to 5.

Besides, every one of these intermediates is a novel compound.

    TABLE 1      Azole derivatives      ##STR29##       Indication in Formula (I) Indication of Compound No. R.sup.1 R.sup.2     X.sub.n A Stereo-isomer Melting point (°C.) NMR Spectral Data     (CDCl.sub.3, δppm)       1 CH.sub.3 CH.sub.3 4-Cl N A-type 113˜114 0.60(s, 3H), 1.00(s,     3H), 1.07˜1.90(m, 5H), 2.33(bs, 2H), 3.53(s, 1H),        4.13(s,     2H), 6.80˜7.23(m, 4H), 7.83(s, 1H), 8.02(s, 1H) 2 CH.sub.3     CH.sub.3 4-Cl N B-type 90˜92 0.82(s, 3H), 1.00(s, 3H), 1.23˜1     .93(m, 4H), 2.07˜2.48(m, 2H), 2.85˜3.07(m, 1H),     3.90(s, 1H), 4.37(s, 2H), 7.03(d, 2H, J=8), 7.25(d, 2H, J=8), 7.97(s,     1H), 8.27(s, 1H) 3 CH.sub.3 CH.sub.3 4-Cl CH A-type 133˜134     0.80(s, 3H), 1.03(s, 3H), 1.13˜2.93(m, 8H), 3.97(s, 2H), 7.02(s,     2H),        6.80˜7.33(m, 4H), 7.60(s, 1H) 4 CH.sub.3 CH.sub.3 4-Cl     CH B-type 133˜134 0.83(s, 3H), 1.03(s, 3H), 1.13˜3.13(m,     8H), 4.03(s, 2H),        6.70˜7.23(m, 6H), 7.63(s, 1H) 5 CH.sub.3     CH.sub.3 4-Br N A-type 129˜130 0.63(s, 3H), 1.00(s, 3H), 1.13.about     .1.93(m, 5H), 2.33(bs, 2H), 3.60(s, 1H),        4.20(s, 2H), 6.93˜7     .50(m, 4H), 7.97(s, 1H), 8.17(s, 1H) 6 CH.sub.3 CH.sub.3 4-Br N B-type     134˜135 0.77(s, 3H), 0.97(s, 3H), 1.20˜3.03(m, 7H), 3.80(s,     1H), 4.33(s, 2H),        6.87˜7.47(m, 4H), 7.93(s, 1H), 8.20(s,     1H) 7 CH.sub.3 CH.sub.3 4-Br CH A-type 149˜150 0.80(s, 3H),     1.03(s, 3H), 1.13˜2.53(m, 8H), 4.00(s, 2H),        6.80˜7.50(     m, 6H), 7.63(s, 1H) 8 CH.sub.3 CH.sub.3 4-Br CH B-type 134˜135     0.83(s, 3H), 1.03(s, 3H), 1.17˜2.97(m, 8H), 4.03(s, 2H),     6.70˜7.40(m, 6H), 7.57(s, 1H) 9 CH.sub.3 CH.sub.3 4-F N A-type     135˜136 0.67(s, 3H), 1.03(s, 3H), 1.17˜2.42(m, 4H), 2.50(bs,     3H), 3.63(s, 1H),        4.23(s, 2H), 6.73˜7.33(m, 4H), 7.93(s,     1H), 8.13(s, 1H) 10 CH.sub.3 CH.sub.3 4-F N B-type 134˜135 0.80(s,     3H), 1.02(s, 3H), 1.27˜3.10(m, 7H), 3.90(m, 1H), 4.37(s, 2H),       6.73˜7.27(m, 4H), 7.97(s, 1H), 8.27(s, 1H) 11 CH.sub.3 CH.sub.3     4-F CH A-type 131˜133 0.83(s, 3H), 1.07(s, 3H), 0.90˜2.00(m,     5H), 2.25(bs, 2H), 2.57(bs, 1H),        4.03(s, 2H), 6.73˜7.27(m,     6H), 7.67(s, 1H) 12 CH.sub.3 CH.sub.3 4-F CH B-type 104˜106     0.87(s, 3H), 1.03(s, 3H), 1.17˜3.03(m, 8H), 4.10(s, 2H),     6.70˜7.27(m, 6H), 7.73(bs, 1H) 13 CH.sub.3 CH.sub.3 2,4-Cl.sub.2 N     A-type 126˜127 0.56(s, 3H), 1.01(s, 3H), 0.79˜2.79(m, 5H),     2.66(bs, 2H), 3.97(s, 1H),        4.27(s, 2H), 7.2(bs, 2H), 7.28(bs,     1H), 7.92(s, 1H), 8.12(s, 1H) 14 CH.sub.3 CH.sub.3 2,4-Cl.sub.2 N B-type     108˜110 0.80(s, 3H), 1.02(s, 3H), 1.25˜1.88(m, 4H), 2.33.abou     t.3.03(m, 2H), 3.75(s, 1H),        4.37(s, 2H), 7.08˜7.37(m, 3H),     7.93(s, 1H), 8.23(s, 1H) 15 CH.sub.3 CH.sub.3 2,4-Cl.sub.2 CH A-type     131˜132 0.70(s, 3H), 1.03(s, 3H), 1.16˜2.65(m, 5H), 2.53(bs,     2H), 2.72(s, 1H),        4.01(s, 2H), 6.99(s, 1H), 7.03(bs, 1H), 7.24(s,     1H), 7.58(s, 1H) 16 CH.sub.3 H 4-Cl N A-type 100˜102 0.74(d, 3H,     J=6), 1.00˜2.27(m, 6H), 2.49(d, 2H, J=6.4), 3.07(s, 1H),     4.20(s, 2H), 7.03(d, 2H, J=8.4), 7.22(d, 2H, J=8.4), 7.95(s, 1H),     8.08(s, 1H) 17 CH.sub.3 H 4-Cl CH A-type 118˜119 0.85(d, 3H,     J=5.8), 1.07˜2.23(m, 6H), 2.51(bd, 2H, J=6.4), 3.34(bs, 1H),      3.95(s, 2H), 6.95(s, 1H), 6.98(d, 2H, J=8), 7.01(s, 1H), 7.18(d, 2H,     J=8),        7.48(s, 1H) 18 H CH.sub.3 4-Cl N A-type 75˜76 0.99(d,     3H, J=6.4), 1.28˜2.24(m, 6H), 2.28˜2.58(m, 2H), 3.60(s, 1H),     3.99(d, 1H, J=14),        4.39(d, 1H, J=14), 6.97(d, 2H, J=9), 8.00(s,     1H), 8.18(s, 1H), 7.24(d, 2H, J=9) 19 H CH.sub.3 4-Cl N B-type 79˜8     1 0.80(d, 3H, J=6.4), 0.99˜2.56(m, 7H), 2.73˜3.39(m, 1H),     3.90(bs, 1H), 4.11(d, 1H, J=14),        4.38(d, 1H, J=14), 7.04(d, 2H,     J=9.4), 7.26(d, 2H, J=9.4), 7.92(s, 1H), 8.22(s, 1H) 20 CH.sub.3 H 4-Cl     N B-type Oily 0.88(d, 3H, J=6.6), 1.05˜2.45(m, 7H), 2.62˜2.92     (m, 1H), 3.85˜4.25(b, 1H, 0H), 4.31(s, 2H),       material 6.98(d,     2H, J=8.8), 7.22(d, 2H, J=8.8), 7.95(s, 1H), 8.26(s, 1H) 21 CH.sub.3     CH.sub.3 H N A-type Oily 0.63(s, 3H), 1.03(s, 3H), 1.13˜2.83(m,     7H), 3.57(s, 1H), 4.23(s, 2H), 7.23(s, 5H),       material 8.00(s, 1H),     8.17(s, 1H) 22 CH.sub.3 CH.sub.3 H CH A-type 128˜130 0.77(s, 3H),     1.03(s, 3H), 1.10˜2.17(m, 5H), 1.97(s, 1H), 2.17˜2.50(m,     2H),        3.97(s, 2H), 6.87˜7.33(m, 7H), 7.57(s, 1H) 23 CH.sub.3     CH.sub.3 4-CH.sub.3 N A-type 123˜124 0.57(s, 3H), 1.02(s, 3H),     1.10˜2.57(m, 8H), 2.27(s, 3H), 4.20(s, 2H),        7.02(s, 4H),     7.95(s, 1H), 8.13(s, 1H) 24 CH.sub.3 CH.sub.3 4-CH.sub.3 N B-type     114˜115 0.73(s, 3H), 0.98(s, 3H), 1.07˜3.00(m, 7H), 2.25(s,     3H), 3.72(s, 1H),        4.28(s, 2H), 6.93(s, 4H), 7.83(s, 1H), 8.10(s,     1H) 25 CH.sub.3 CH.sub.3 4-CH.sub.3 CH A-type 132˜133 0.75(s, 3H),     1.02(s, 3H), 1.02˜2.42(m, 8H), 2.27(s, 3H), 3.93(s, 2H),     6.98(s, 4H), 7.02(s, 2H), 7.58(s, 1H) 26 CH.sub.3 CH.sub.3 4-CH.sub.3 CH     B-type 130˜131 0.83(s, 3H), 1.07(s, 3H), 1.17˜3.07(m, 8H),     2.27(s, 3H), 4.07(s, 2H),        6.77˜7.20(m, 2H), 6.95(s, 4H),     7.62(s, 1H) 27 CH.sub.3 CH.sub.3 2-F, 4-Cl N A-type 129˜130     0.62(s, 3H), 1.02(s, 3H), 1.13˜2.67(m, 7H), 3.82(s, 1H), 4.21(s,     2H),        6.23˜7.23(m, 3H), 7.89(s, 1H), 8.11(s, 1H) 28 CH.sub.3     CH.sub.3 2-F, 4-Cl CH A-type 152˜154 0.78(s, 3H), 1.02(s, 3H),     1.10˜2.80(m, 8H), 3.98(s, 2H),        6.68˜7.20(m, 5H),     7.57(s, 1H) 29 C.sub.2      H.sub.5 H 4-Cl N A-type 82˜84 0.67˜2.23(m, 11H), 2.43(d,     2H, J=7), 2.93(s, 1H), 4.20(s, 2H),        6.93˜7.33(m, 4H),     7.93(s, 1H), 8.07(s, 1H) 30 H C.sub.2 H.sub.5 4-Cl N A-type 93˜95     0.70˜2.13(m, 11H), 2.13˜2.47(m, 2H), 3.83(s, 1H), 4.00(d,     1H, J=14), 4.30(d, 1H, J=14),        6.88(d, 2H, J=8), 7.18(d, 2H, J=8),     7.93(s, 1H), 8.17(s, 1H) 31 H C.sub.2 H.sub.5 4-Cl N B-type 76˜78     0.67˜3.33(m, 13H), 3.07(d, 1H, J=10), 4.13(d, 1H, J=14), 4.40(d,     1H, J=14),        7.03(d, 2H, J=8), 7.23(d, 2H, J=8), 7.97(s, 1H),     8.18(s, 1H) 32 C.sub.2      H.sub.5 H 4-Cl N B-type 110˜112 0.67˜2.20(m, 12H), 2.73(d,     1H, J=10), 4.15(s, 1H), 4.30(s, 2H), 6.95(d, 2H, J=8),        7.20(d,     2H, J=8), 7.97(s, 1H), 8.18(s, 1H) 33 C.sub.2 H.sub.5 C.sub. 2 H.sub.5     4-Cl N A-type 124˜126 0.67˜1.07(m, 6H), 1.07˜2.40(m,     11H), 3.52(s, 1H), 4.30(s, 2H), 6.87(d, 2H, J=9),        7.18(d, 2H,     J=9), 7.93(s, 1H), 8.18(s, 1H) 34 C.sub.2 H.sub.5 C.sub.2 H.sub.5 4-Cl N     B-type 143˜145 0.87(t, 6H, J=6), 1.10˜1.97(m, 8H), 1.97.about     .2.54(m, 2H), 2.73(d, 1H, J=9), 3.33˜3.70(b, 1H),        4.43(s,     2H), 6.92(d, 2H, J=9), 7.20(d, 2H, J=9), 7.97(s, 1H), 8.27(s, 1H) 35     C.sub.2 H.sub.5 C.sub.2 H.sub.5 4-Cl CH A-type Oily 0.87(t, 6H, J=6),     1.07˜2.50(m, 11H), 3.33(s, 1H), 3.90(d, 1H, J=14),       material     4.18(d, 1H, J=14), 6.70˜7.23(m, 6H), 7.67(s, 1H) 36 C.sub.2     H.sub.5 C.sub.2 H.sub.5 4-Cl CH B-type 143˜145 0.87(t, 6H, J=6),     1.10˜2.33(m, 10H), 2.53˜2.88(m, 2H), 4.13(s, 2H),     6.75˜7.35(m, 6H), 7.70(s, 1H) 37 n-C.sub.3 H.sub.7 H 4-Cl N A-type     83˜85 0.61˜2.26(m, 13H), 2.26˜2.57(m, 2H), 2.51˜2     .81(b, 1H), 4.21(s, 2H),        7.03(d, 2H, J=9), 7.23(d, 2H, J=9),     7.96(s, 1H), 8.07(s, 1H) 38 H n-C.sub.3      H.sub.7 4-Cl N A-type 75˜77 0.65˜1.04(m, 3H), 1.04˜2.1     8(m, 10H), 2.18˜2.48(m, 2H), 3.70(bs, 1H), 3.98(d, 1H, J=14),       4.29(d, 1H, J=14), 6.86(d, 2H, J=8.4), 7.16(d, 2H, J=8.4), 7.94(s,     1H), 8.12(s, 1H) 39 n-C.sub.3 H.sub.7 H 4-Cl CH A-type 115˜117     0.57˜1.04(m, 3H), 1.04˜2.24(m, 10H), 2.43(bs, 2H), 2.55(bs,     1H), 3.96(s, 2H),        6.99(d, 2H, J=8.4), 7.02(bs, 2H), 7.20(d, 2H,     J=8.4), 7.45(bs, 1H) 40 C.sub.2      H.sub.5 H 2,4-Cl.sub.2 N A-type 124˜127 0.63˜2.40(m, 11H),     2.68(d, 2H, J=6), 3.10(s, 1H), 4.23(s, 2H),        7.13(bs, 2H),     7.30(bs, 1H), 7.93(s, 1H), 8.10(s, 1H) 41 C.sub.2 H.sub.5 H 2,4-Cl.sub.2     CH A-type 111˜113 0.67˜2.27(m, 11H), 2.50(d, 2H, J=7),     2.63(bs, 1H), 3.98(s, 2H),        6.90(bs, 2H), 6.97(bs, 2H), 7.37(bs,     1H), 7.50(bs, 1H) 42 C.sub.2      H.sub.5 H 4-F N A-type 73˜74 0.62˜2.19(m, 11H), 2.30˜2     .51(m, 2H), 2.62(s, 1H), 4.15(s, 2H),        6.64˜7.23(m, 4H),     7.88(s, 1H), 7.99(s, 1H) 43 C.sub.2      H.sub.5 H 4-F CH A-type 111˜113 0.66˜2.07(m, 11H), 2.19(s,     1H), 2.35˜2.60(m, 2H),        3.93(s, 2H), 6.63˜7.20(m, 6H),     7.41(bs, 1H) 44 C.sub.2      H.sub.5 H 4-Br N A-type 80˜82 0.68˜2.25(m, 11H), 2.43(d,     2H, J=7), 2.85(s, 1H), 4.22(s, 2H),        7.02(d, 2H, J=8), 7.37(d, 2H,     J=7), 7.93(s, 1H), 8.08(s, 1H) 45 C.sub.2 H.sub.5 H 4-Br CH A-type     117˜119 0.60˜2.50(m, 11H), 2.33˜3.02(m, 2H), 3.18(bs,     1H), 4.00(s, 2H),        6.88˜7.02(m, 2H), 7.03˜7.35(m, 3H),     7.48(bs, 1H) 46 C.sub.2 H.sub.5 H 4-C.sub.6      H.sub.5 N A-type 107˜109 0.56˜2.34(m, 11H), 2.40˜2.60(     m, 2H), 2.65(s, 1H), 4.20(s, 2H),        7.05˜7.70(m, 9H), 7.95(s,     1H), 8.05(s, 1H) 47 C.sub.2 H.sub.5 H 4-C.sub.6 H.sub.5 CH A-type     169˜170 0.66˜2.28(m, 11H), 2.01(s, 1H), 2.45˜2.72(m,     2H),        3.96(s, 2H), 6.85˜7.63(m, 12H) 48 C.sub.2 H.sub.5 H     4-t-C.sub.4 H.sub.9 N A-type Oily 0.85(t, 3H, J=7), 1.29(s, 9H),     0.90˜1.90(m, 8H), 2.41(dd, 1H, J=14, 10),       material 2.49(dd,     1H, J=14, 5), 4.23(s, 2H), 7.07(d, 2H, J=8.3), 7.28(d, 2H, J=8.3),      7.96(s, 1H), 8.01(s, 1H) 49 C.sub.2 H.sub.5 H 4-t-C.sub.4 H.sub.9 CH     A-type 132˜133 0.67˜2.83(m, 14H), 1.32(s, 9H), 4.08(s, 2H),           6.97˜7.53(m, 6H), 7.58(s, 1H) 50 i-C.sub.3 H.sub.7 H 4-Cl N     A-type 91˜92 0.95(d, 3H, J=7), 0.97(d, 3H, J=7), 1.17˜2.93(m,      10H), 4.12(d, 1H, J=14),        4.41(d, 1H, J=14), 6.87˜7.40(m,     4H), 7.97(s, 1H), 8.13(s, 1H) 51 n-C.sub.5 H.sub.11 H 4-Cl N A-type Oily     0.86(t, 3H, J=6.8), 0.90˜1.98(m, 14H), 2.38(dd, 1H, J=13.4, 9.3),          material 2.46(dd, 1H, J=13.4, 5.4), 2.57(s, 1H), 4.23(s, 2H),     7.06(d, 2H, J=8.3),        7.22(d, 2H, J=8.3), 7.97(s, 1H), 8.08(s, 1H)     52 n-C.sub.5 H.sub.11 H 4-Cl CH A-type 92˜95 0.87(t, 3H, J=6.8),     1.05˜1.95(m, 14H), 2.43(dd, 1H, J=13.7, 10.3),        2.56(dd, 1H,     J=13.7, 4.4), 3.47(s, 1H), 3.99(s, 2H), 6.94(s, 1H), 7.05(d, 2H, J=8.3),            7.06(s, 1H), 7.22(d, 2H, J=8.3), 7.48(s, 1H) 53 C.sub.2 H.sub.5 H     4-Cl CH B-type 138˜140 0.57˜0.98(m, 3H), 0.98˜2.17(m,     9H), 2.73(d, 1H, J=10),        3.43(bs, 1H), 4.03(s, 2H), 6.83˜7.03     (m, 6H), 7.68(bs, 1H) 54 H n-C.sub.5 H.sub.11 4-Cl N A-type Oily 0.88(t,     3H, J=6.8), 1.00˜1.94(m, 14H), 2.31(m, 2H), 3.70(bs, 1H),     material 4.05(d, 1H, J=13.7), 4.26(d, 1H, J=13.7), 6.89(d, 2H, J=8.3),     7.17(d, 2H, J=8.3),        7.99(s, 1H), 8.15(s, 1H) 55 CH.sub.3 CH.sub.3     4-C.sub.6 H.sub.5 N A-type 122˜124 0.63(s, 3H), 1.02(s, 3H),     1.10˜2.13(m, 4H), 2.47(bs, 3H), 3.62(s, 1H), 4.23(s, 2H),     7.10˜7.73(m, 9H), 7.97(s, 1H), 8.17(s, 1H) 56 CH.sub.3 CH.sub.3     4-C.sub.6 H.sub.5 N B-type 116˜118 0.77(s, 3H), 0.98(s, 3H),     1.10˜2.80(m, 5H), 2.33(d, 1H, J=9), 2.98(d, 1H, J=9),     3.88(s, 1H), 4.33(s, 2H), 7.07˜7.73(m, 9H), 7.97(s, 1H), 8.25(s,     1H) 57 CH.sub.3 CH.sub.3 4-C.sub.6 H.sub.5 CH A-type 162˜163     0.80(s, 3H), 1.03(s, 3H), 1.12˜2.08(m, 4H), 2.37(bs, 3H), 2.43(s,     1H), 4.00(s, 2H),        6.88˜7.78(m, 12H) 58 CH.sub.3 CH.sub.3     4-C.sub.6 H.sub.5 CH B-type 165˜167 0.85(s, 3H), 1.03(s, 3H),     1.13˜2.77(m, 5H), 2.30(d, 1H, J=9), 2.95(d, 1H, J=9),     3.60(s, 1H), 4.13(s, 2H), 6.90˜7.87(m, 12H) 59 i-C.sub.3 H.sub.7 H     4-Cl CH A-type Oily 0.97(d, 3H, J=7), 1.00(d, 3H, J=7), 1.23˜2.53(m     , 10H), 3.90(d, 1H, J=14),       material 4.17(d, 1H, J=14), 6.90˜7     .43(m, 6H), 7.53(bs, 1H) 60 CH.sub.3 CH.sub.3 4-t-C.sub.4 H.sub.9 N     A-type 107˜108 0.62(s, 3H), 1.01(s, 3H), 1.27(s, 9H), 1.17˜2.     00(m, 5H), 2.17˜2.67(m, 2H), 3.50(s, 1H),        4.22(s, 2H),     7.00(d, 2H, J=8.4), 7.25(d, 2H, J=8.4), 7.92(s, 1H), 8.12(s, 1H) 61     CH.sub.3 CH.sub.3 4-t-C.sub.4 H.sub.9 CH A-type 167˜168 0.78(s,     1H), 1.02(s, 3H), 1.29(s, 9H), 1.14˜2.10(m, 5H), 2.14˜2.57(m,      2H), 2.40(s, 1H),        3.97(s, 2H), 6.96(d, 2H, J=8.4), 7.03(bs, 2H),     7.23(d, 2H, J=8.4), 7.59(bs, 1H) 62 H i-C.sub.3 H.sub.7 4-Cl N B-type     Oily 0.60˜3.17(m, 15H), 3.43(bs, 1H), 4.20(s, 2H), 6.9(d, 2H,     J=8),       material 7.15(d, 2H, J=8), 7.87(s, 1H), 8.07(s, 1H) 63 H     i-C.sub.3 H.sub.7 4-Cl N A-type 102˜103 0.70˜2.33(m, 15H),     3.47(bs, 1H), 3.97(d, 1H, J=14), 4.38(d, 1H, J=14),        6.73(d, 2H,     J=8), 7.10(d, 2H, J=8), 7.93(s, 1H), 8.10(s, 1H) 64 H i-C.sub.3 H.sub.7     4-Cl CH A-type 146˜147 0.83˜2.43(m, 16H), 3.73(d, 1H, J=14),     4.22(d, 1H, J=14),        6.60˜7.27(m, 6H), 7.53(s, 1H) 65     i-C.sub.3 H.sub.7 H 4-Cl N B-type 120˜121 0.70˜2.63(m, 15H),     3.70(bs, 1H), 4.33(s, 2H), 7.00(d, 2H, J=8),        7.27(d, 2H, J=8),     8.07(s, 1H), 8.40(s, 1H) 66 n-C.sub.4 H.sub.9 H 4-Cl CH A-type Oily     0.57˜2.67(m, 17H), 3.05(s, 1H), 3.95(s, 2H),       material     6.68˜7.25(m, 6H), 7.38(bs, 1H) 67 H n-C.sub.4 H.sub.9 4-Cl N     A-type 94˜95 0.63˜2.43(m, 17H), 3.67(s, 1H), 3.95(d, 1H,     J=14), 4.25(d, 1H, J=14),        6.77(d, 2H, J=8), 7.07(d, 2H, J=8),     7.83(s, 1H), 8.02(s, 1H) 68 H n-C.sub.4 H.sub.9 4-Cl N B-type Oily     0.60˜2.33(m, 16H), 2.90˜3.20(m, 1H), 3.30(s, 1H), 4.22(s,     2H),       material 6.88(d, 2H, J=8), 7.12(d, 2H, J=8), 7.83(s, 1H),     8.02(s, 1H) 69 i-C.sub.4 H.sub.9 H 4-Cl N A-type Oily 0.78(d, 3H, J=6),     0.88(d, 3H, J=6), 1.07˜2.27(m, 9H), 2.33˜2.67(m, 3H),     material 4.22(s, 2H), 7.00(d, 2H, J=9), 7.2(d, 2H, J=9), 7.93(s, 1H),     8.05(s, 1H) 70 i-C.sub.4 H.sub.9 H 4-Cl CH A-type Oily 0.81(d, 3H, J=6),     0.88(d, 3H, J=6), 1.03˜2.10(m, 9H), 2.26˜2.70(m, 2H),     material 3.88(s, 1H), 4.00(s, 2H), 6.70˜7.30(m, 6H), 7.46(s, 1H)     71 n-C.sub.4 H.sub.9 H 4-Cl N A-type Oily 0.60˜2.63(m, 17H),     2.80(s, 1H), 4.23(s, 2H), 7.07(d, 2H, J=8), 7.27(d, 2H, J=8),     material 8.00(s, 1H), 8.13(s, 1H) 72 Isomer CH.sub.3 C.sub.2 H.sub.5     4-Cl N A-type Mixture 0.57˜1.02(m, 6H), 1.12˜2.55(m, 9H),  a          of 72-a 3.55, 3.67(2s, 1H), 4.20(bs, 2H),  Isomer C.sub.2 H.sub.5     CH.sub.3 4-Cl N A-type & 72-b 6.95(d, 2H, J=9), 7.18(d, 2H, J=9)  b      98˜101 7.92(s, 1H), 8.12(s, 1H) 73 Isomer CH.sub.3 C.sub.2     H.sub.5 4-Cl N B-type Mixture 0.67˜1.05(m, 6H), 1.05˜3.12(m,     9H),  a      of 73-a 3.77, 3.92(2s, 1H), 4.35(s, 2H),  Isomer C.sub.2     H.sub.5 CH.sub.3 4-Cl N B-type & 73-b 6.95(d, 2H, J=8), 7.18(d, 2H,     J=8),  b      117˜119 7.90(s, 1H), 8.15, 8.15(2s, 1H) 74 Isomer     CH.sub.3 C.sub.2 H.sub.5 4-Cl CH B-type Mixture 0.63˜1.08(m, 6H),     1.08˜3.07(m, 9H),  a      of 74-a 3.33(s, 1H), 4.12(bs, 2H),     Isomer C.sub. 2      H.sub.5 CH.sub.3 4-Cl CH B-type & 74-b 6.80˜7.30(m, 6H), 7.70(bs,     1H)  b      122˜127 75 CH.sub.3 CH.sub.3 4-t-C.sub.4 H.sub.9 N     B-type Oily 0.77(s, 3H), 1.01(s, 3H), 1.28(s, 9H), 1.39˜2.11(m,     5H),       material 2.12˜2.54(m, 2H), 3.78(bs, 1H), 4.34(s, 2H),     6.95(d, 2H, J=8.4),        7.20(d, 2H, J=8.4), 7.88(s, 1H), 8.14(s, 1H)     76 CH.sub.3 CH.sub.3 4-t-C.sub.4 H.sub.9 CH B-type 132˜133 0.84(s,     3H), 1.06(s, 3H), 1.30(s, 9H), 1.43˜3.10(m, 8H),        4.13(s,     2H), 6.87(bs, 1H), 7.01(d, 2H, J=8.4), 7.19(bs, 1H),        7.29(d, 2H,     J=8.4), 7.73(bs, 1H)

                                      TABLE 2                                     __________________________________________________________________________    Oxirane Derivative                                                             ##STR30##                                                                                       Indi-                                                                         ca-                                                                           tion                                                                          of                                                                            Ster-                                                      Com-               eo-                                                        pound                                                                             Indication in formula (II)                                                                   iso-                                                                             Physical                                                No. R.sup.1                                                                            R.sup.2                                                                            X.sub.n                                                                            mer                                                                              property                                                                           NMR Spectral data (CDCl.sub.3,                     __________________________________________________________________________                               δppm)                                        77  CH.sub.3                                                                           CH.sub.3                                                                           4-Cl A- Oily 0.83(s, 3H), 0.95(s, 3H), 1.33˜1.73(m,                                  4H), 2.33˜2.53(m, 3H), 2.52(d, 1H,                                      J=4),                                                                 type                                                                             material                                                                           2.67(d, 1H, J=4), 7.03(d, 2H, J=8), 7.23(d,                                   2H, J=8)                                           78  CH.sub.3                                                                           CH.sub.3                                                                           4-Cl B- Oily 0.87(s, 3H), 0.93(s, 3H), 1.45˜1.73(m,                                  4H), 2.13˜2.70(m, 3H), 2.60(d, 1H, J=4),                        type                                                                             material                                                                           2.83(d, 1H, J=4), 7.02(d, 2H, J=8), 7.23(d,                                   2H, J=8)                                           79  CH.sub.3                                                                           CH.sub.3                                                                           4-Br A- Oily 0.83(s, 3H), 0.93(s, 3H), 1.17˜1.73(m,                                  4H), 2.17˜2.67(m, 3H), 2.50(d, 1H, J=4),                        type                                                                             material                                                                           2.60(s, 1H, J=4), 6.80˜7.33(m, 4H)           80  CH.sub.3                                                                           CH.sub.3                                                                           4-Br B- Oily 0.87(s, 3H), 0.93(s, 3H), 1.20˜2.73(m,                                  7H), 2.60(d, 1H, J=4), 2.80(d, 1H, J=4),                              type                                                                             material                                                                           6.80˜7.47(m, 4H)                             81  CH.sub.3                                                                           CH.sub.3                                                                           4-F  A- Oily 0.80(s, 3H), 0.90(s, 3H), 1.00˜2.00(m,                                  4H), 2.00˜2.67(m, 5H),                                                  6.70˜7.23(m, 4H)                                                type                                                                             material                                                82  CH.sub.3                                                                           CH.sub.3                                                                           4-F  B- Oily 0.88(s, 3H), 0.93(s, 3H), 1.03˜2.00(m,                                  4H), 2.00˜2.93(m, 5H),                                                  6.70˜7.27(m, 4H)                                                type                                                                             material                                                83  CH.sub.3                                                                           CH.sub.3                                                                           2.4-Cl.sub.2                                                                       A- Oily 0.85(s, 3H), 0.92(s, 3H), 1.27˜1.82(m,                                  4H), 2.28˜2.78(m, 5H),                                                  6.92˜7.28(m, 3H)                                                type                                                                             material                                                84  CH.sub.3                                                                           CH.sub.3                                                                           2.4-Cl.sub.2                                                                       B- Oily 0.87(s, 3H), 0.97(s, 3H), 1.48˜1.72(m,                                  4H), 2.33˜2.77(m, 3H), 2.62(d, 1H, J=4),                                9                                                                     type                                                                             material                                                                           2.85(d, 1H, J=4), 7.05˜7.37(m, 3H)           85  CH.sub.3                                                                           H    4-Cl A- Oily 0.80(d, 3H, J=6), 1.14˜2.51(m, 6H),                                     2.31˜2.51(b, 2H), 2.63(s, 2H),                                  type                                                                             material                                                                           7.00(d, 2H, J=9). 7.19(d, 2H, J=9)                 86  H    CH.sub.3                                                                           4-Cl A- Oily 0.89(d, 3H, J=6), 0.85˜2.68(m, 6H),                                     2.32˜2.42(b, 2H), 2.47(d, 1H, J=4.6),                           type                                                                             material                                                                           2.78(d, 1H, J=4.6), 6.75˜7.28(m, 4H)         87  H    CH.sub.3                                                                           4-Cl B- Oily 0.81(d, 3H, J=6), 0.93˜3.00(m, 8H),                                     2.54(d, 1H, J=4.6),                                                   type                                                                             material                                                                           2.79(d, 1H, J=4.6), 6.80˜7.33(m, 4H)         88  CH.sub.3                                                                           H    4-Cl B- Oily 1.09(d, 3H, J=6), 0.83˜3.26(m, 10H),                                    6.95(d, 2H, J=9),                                                     type                                                                             material                                                                           7.14(d, 2H, J=9)                                   89  CH.sub.3                                                                           CH.sub.3                                                                           H    A- Oily 0.73˜2.07(m, 5H), 0.87(s, 3H), 0.97(s,                                  3H), 2.27˜2.77(m, 2H),                                          type                                                                             material                                                                           2.55(d, 1H, J=4), 2.67(d, 1H, J=4), 7.23(s,                                   5H)                                                90  CH.sub.3                                                                           CH.sub.3                                                                           4-CH.sub.3                                                                         A- Oily 0.83(s, 3H), 0.97(s, 3H), 1.17˜1.97(m,                                  5H), 2.17˜2.77(m, 2H), 2.27(s, 3H),                             type                                                                             material                                                                           2.55(d, 1H, J=4), 2.65(d, 1H, J=4), 7.00(s,                                   4H)                                                91  CH.sub.3                                                                           CH.sub.3                                                                           4-CH.sub.3                                                                         B- Oily 0.87(s, 3H), 0.93(s, 3H), 1.47˜1.77(m,                                  5H), 2.17˜2.97(m, 2H), 2.30(s, 3H),                             type                                                                             material                                                                           2.65(d, 1H, J=4), 2.87(d, 1H, J=4), 7.07(s,                                   4H)                                                92  CH.sub.3                                                                           CH.sub.3                                                                           2-F-4-Cl                                                                           A- Oily 0.83(s, 3H), 0.93(s, 3H), 1.09˜2.79(m,                                  9H), 6.83˜7.15(m, 3H)                                           type                                                                             material                                                93  C.sub.2 H.sub.5                                                                    H    4-Cl A- Oily 0.60˜2.83(m, 11H), 2.43(bs, 2H), 2.65(s,                                2H), 6.92˜7.33(m, 4H)                                           type                                                                             material                                                94  H    C.sub.2 H.sub.5                                                                    4-Cl A- Oily 0.67˜2.77(m, 11H), 2.37(bs, 2H), 2.53(d,                                1H), J=4),                                                            type                                                                             material                                                                           2.85(d, 1H, J=4), 6.87˜7.33(m, 4H)           95  H    C.sub.2 H.sub.5                                                                    4-Cl B- Oily 0.60˜2.92(m, 13H), 2.57(d, 1H, J=4),                                    2.82(d, 1H, J=4), 6.87˜7.30(m, 4H)                              type                                                                             material                                                96  C.sub.2 H.sub.5                                                                    H    4-Cl B- Oily 0.67˜2.85(m, 13H), 2.75(s, 2H),                                         6.88˜7.33(m, 4H)                                                type                                                                             material                                                97  C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                    4-Cl A- Oily 0.57˜1.03(m, 6H), 1.03˜2.05(m,                                    9H), 2.38(bs, 2H),                                                    type                                                                             material                                                                           2.57(d, 1H, J=4), 2.67(d, 1H, J=4),                                           6.90˜7.30(m, 4H)                             98  C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                    4-Cl B- Oily 0.63˜1.03(m, 6H), 1.03˜1.90(m,                                    9H), 2.07˜2.50(m, 2H), 2.62(d, 1H, J=4),                        type                                                                             material                                                                           2.75(d, 1H, J=4), 6.83˜7.23(m, 4H)           99  n-C.sub.3 H.sub.7                                                                  H    4-Cl A- Oily 0.59˜1.02(m, 3H), 1.02˜2.29(m,                                    10H), 2.29˜2.52(m, 2H), 2.68(s, 2H),                            type                                                                             material                                                                           7.05(d, 2H, J=9), 7.25(d, 2H, J=9)                 100 H    n-C.sub.3 H.sub.7                                                                  4-Cl A- Oily 0.62˜1.03(m, 3H), 1.03˜2.32(m,                                    10H), 2.32˜2.48(b, 2H), 2.53(d, 1H,                                     J=4.4),                                                               type                                                                             material                                                                           2.86(d, 1H, J=4.4), 7.03(d, 2H, J=9), 7.22(d,                                 2H, J=9)                                           101 C.sub.2 H.sub.5                                                                    H    2, 4-Cl.sub.2                                                                      A- Oily 0.67˜3.10(m, 13H), 2.70(s, 2H), 7.10(m,                                 2H), 7.28(m, 1H)                                                      type                                                                             material                                                102 C.sub.2 H.sub.5                                                                    H    4-F  A- Oily 0.65˜2.50(m, 13H), 2.62(s, 2H),                                         6.60˜7.24(m, 4H)                                                type                                                                             material                                                103 C.sub.2 H.sub.5                                                                    H    4-Br A- Oily 0.67˜2.13(m, 11H), 2.42(m, 2H), 2.65(s,                                 2H), 6.98(d, 2H, J=8), 7.35(d, 2H, J=8)                               type                                                                             material                                                104 C.sub.2 H.sub.5                                                                    H    4-C.sub.6 H.sub.5                                                                  A- Solid                                                                              0.63˜2.58(m, 13H), 2.66(s, 2H),                                         7.04˜7.68(m, 9H)                                                type                                                                             mp:69˜71° C.                               105 C.sub.2 H.sub.5                                                                    H    4-t-C.sub.4 H.sub.9                                                                A- Oily 0.69˜2.55(m, 13H), 1.27(s, 9H), 2.65(s,                                 2H), 6.93˜7.42(m, 4H)                                           type                                                                             material                                                106 i-C.sub.3 H.sub.7                                                                  H    4-Cl A- Oily 0.85(d, 6H, J=7), 1.00˜2.83(m, 9H),                                     2.63(s, 2H), 6.90˜7.33(m, 4H)                                   type                                                                             material                                                107 n-C.sub.5 H.sub.11                                                                 H    4-Cl A- Oily 0.87(t, 3H, J=6.8), 1.00˜2.56(m, 16H),                                  2.67(d, 1H, J=4.4), 2.71(d, 1H, J=4.4),                               type                                                                             material                                                                           7.08(d, 2H, J=8.3), 7.22(d, 2H, J=8.3)             108 H    n-C.sub.5 H.sub.11                                                                 4-Cl A- Oily 0.87(t, 3H, J=6.8), 1.00˜2.54(m, 16H),                                  2.56(d, 1H, J=4.4), 2.88(d, 1H, J=4.4),                               type                                                                             material                                                                           7.09(d, 2H, J=8.3), 7.23(d, 2H, J=8.3)             109 CH.sub.3                                                                           CH.sub.3                                                                           4-t-C.sub.4 H.sub.9                                                                A- Oily 0.80(s, 3H), 0.94(s, 3H), 1.28(s, 9H),                                        1.41˜1.96(m, 4H), 2.18˜2.48(b,                                    3H),                                                                  type                                                                             material                                                                           2.55(d, 1H, J=4.4), 2.64(d, 1H, J=4.4),                                       7.02(d, 2H, J=8), 7.18(d, 2H, J=8)                 110 CH.sub.3                                                                           CH.sub.3                                                                           4-t-C.sub.4 H.sub.9                                                                B- Oily 0.87(s, 3H), 0.94(s, 3H), 1.28(s, 9H),                                        1.40˜1.93(m, 4H), 2.20˜2.76(m,                                    3H),                                                                  type                                                                             material                                                                           2.60(d, 1H, J=4.4), 2.84(d, 1H, J=4.4),                                       7.02(d, 2H, J=8), 7.27(d, 2H, J=8)                 111 CH.sub.3                                                                           CH.sub.3                                                                           4-C.sub.6 H.sub.5                                                                  A- Oily 0.83(s, 3H), 0.92(s, 3H), 1.10˜2.18(m,                                  4H), 2.47(bs, 3H), 2.50(d, 1H, J=4),                                  type                                                                             material                                                                           2.63(d, 1H, J=4), 6.97˜7.63(m, 9H)           112 CH.sub.3                                                                           CH.sub.3                                                                           4-C.sub.6 H.sub.5                                                                  B- Oily 0.85(s, 3H), 0.93(s, 3H), 1.20˜1.97(m,                                  4H), 1.97˜2.90(m, 3H), 2.57(d, 1H, J=4),                        type                                                                             material                                                                           2.82(d, 1H, J=4), 6.97˜7.58(m, 9H)           113 H    i-C.sub.3 H.sub.7                                                                  4-Cl A- Oily 0.82(d, 3H, J=6), 0.85(d, 3H, J=6),                                           0.97˜2.73(m, 9H),                                               type                                                                             material                                                                           2.60(d, 1H, J=4), 2.88(d, 1H, J=4),                                           6.93˜7.37(m, 4H)                             114 H    i-C.sub.3 H.sub.7                                                                  4-Cl B- Oily 0.67˜1.03(m, 6H), 1.03˜2.77(m,                                    9H), 2.50(d, 1H, J=4),                                                type                                                                             material                                                                           2.83(d, 1H, J=4), 6.90˜7.33(m, 4H)           115 i-C.sub.3 H.sub.7                                                                  H    4-Cl B- Oily 0.87(d, 3H, J=6), 0.90(d, 3H, J=6),                                           1.10˜3.20(m, 9H),                                               type                                                                             material                                                                           2.87(s, 2H), 6.90˜7.40(m, 4H)                116 n-C.sub.4 H.sub.9                                                                  H    4-Cl A- Oily 0.63˜2.80(m, 17H), 2.67(s, 2H),                                         6.93˜7.37(m, 4H)                                                type                                                                             material                                                117 H    n-C.sub.4 H.sub.9                                                                  4-Cl A- Oily 0.50˜2.70(m, 17H), 2.50(d, 1H, J=4),                                    2.83(d, 1H, J=4), 6.90˜7.30(m, 4H)                              type                                                                             material                                                118 H    n-C.sub.4 H.sub.9                                                                  4-Cl B- Oily 0.63˜2.73(m, 17H), 2.53(d, 1H, J=4),                                    2.77(d, 1H, J=4), 6.80˜7.23(m, 4H)                              type                                                                             material                                                119 i-C.sub.4 H.sub.9                                                                  H    4-Cl A- Oily 0.78(d, 3H, J=7), 0.88(d, 3H, J=7),                                           1.00˜2.27(m, 9H),                                               type                                                                             material                                                                           2.27˜2.50(m, 2H), 2.63(s, 2H),                                          6.87˜7.33(m, 4H)                             120                                                                           Isomer                                                                            CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    4-Cl A- Mixture                                                                            0.68˜0.97(m, 6H), 0.97˜1.85(m,                                    6H),                                               a                  type                                                                             of 120a                                                                            2.15˜2.75(m, 5H),                            Isomer                                                                            C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           4-Cl A- a 120b                                                                             7.00(d, 2H, J=8),                                  b                  type                                                                             Oily 7.17(d, 2H, J=8)                                                         material                                                121                                                                           Isomer                                                                            CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    4-Cl B- Mixture                                                                            0.67˜1.00(m, 6H), 1.00˜1.90(m,                                    6h),                                               a                  type                                                                             of 121a                                                                            2.13˜2.90(m, 5H), 6.97(d, 2H, J=8),          Isomer                                                                            C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           4-Cl A- a 121b                                                                             7.17(d, 2H, J=8),                                  b                  type                                                                             Oily                                                                          material                                                __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    (methylenecyclopentane Derivatives)                                            ##STR31##                                                                    Compound                                                                            Indication in Formula (III)                                                                 Physical                                                  No.   R.sup.1                                                                            R.sup.2                                                                           X.sub.n                                                                            property                                                                            NMR Spectral Data (CDCl.sub.3,                      __________________________________________________________________________                              δppm)                                         122   CH.sub.3                                                                           CH.sub.3                                                                          4-Cl Oily  1.03(s, 3H), 1.08(2, 3H), 1.28˜1.85(m,                                  4H0, 2.35˜3.12(m, 3H), 4.75˜4.95(m,                               2H),                                                                    material                                                                            7.07(d, 2H, J=8), 7.27(d, 2H, J=8)                  123   CH.sub.3                                                                           CH.sub.3                                                                          4-Br Oily  1.00(s, 3H), 1.03(s, 3H), 1.13˜1.77(m,                                  5H), 2.30˜3.10(m, 2H), 4.63˜4.80(m,                               2H),                                                                    material                                                                            6.83˜7.40(m, 4H)                              124   CH.sub.3                                                                           CH.sub.3                                                                          4-F  Oily  1.00(s, 3H), 1.07(s, 3H), 1.13˜2.00(m,                                  4H), 2.00˜3.13(m, 3H), 4.72˜4.90(m,                               2H),                                                                    material                                                                            6.70˜7.28(m, 4H)                              125   CH.sub.3                                                                           CH.sub.3                                                                          2, 4-Cl.sub.2                                                                      Oily  1.07(s, 3H × 2), 1.27˜1.80(m, 4H),                                2.43˜3.18(m, 3H), 4.72˜4.88(m, 2H),                         material                                                                            7.05˜7.37(m, 3H)                              126   CH.sub.3                                                                           CH.sub.3                                                                          4-CH.sub.3                                                                         Oily  1.03(s, 3H), 1.07(s, 3H), 0.66˜1.90(m,                                  5H), 2.17˜3.13(m, 2H),                                            material                                                                            4.83(bs, 2H), 7.07(s, 4H)                           127   CH.sub.3                                                                           CH.sub.3                                                                          4-t-C.sub.4 H.sub.9                                                                Oily  1.03(s, 3H), 1.08(s, 3H), 1.30(s, 9H),                                        1.36˜1.86(m, 4H), 2.20˜3.13(m, 3H),                         material                                                                            4.76˜4.93(bs, 2H), 7.07(d, 2H, J=8),                                    7.27(d, 2H, J=8)                                    128   CH.sub.3                                                                           CH.sub.3                                                                          4-C.sub.6 H.sub.5                                                                  Oily  1.03(s, 3H), 1.10(s, 3H), 1.10˜1.92(m,                                  4H), 2.17˜3.17(m, 3H),                                            material                                                                            4.83(bs, 2H), 7.08˜7.70(m, 9H)                129   C.sub.2 H.sub.5                                                                    H   4-Cl Oily  0.93(t, 3H, J=7), 1.08˜3.08(m, 10H),                                    4.76˜4.93(m, 2H), 6.97˜7.37(m, 4H)                          material                                                  130   i-C.sub.3 H.sub.7                                                                  H   4-Cl Oily  0.60(d, 3H, J=8), 0.70(d, 3H, J=8),                                           0.87˜2.97(m, 9H), 4.57˜4.83(m, 2H),                         material                                                                            6.77˜7.20(m, 4H)                              131   C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   4-Cl Oily  0.63˜1.05(m, 6H); 1.05˜1.93(m, 8H),                               2.13˜3.13(m, 3H),                                                 material                                                                            4.80(dd, 2H, J=12.2), 6.95˜7.33(m, 4H)        132   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   4-Cl Oily  0.63˜1.10(m, 6H), 1.10˜1.80(m, 6H),                               2.23˜3.13(m, 3H), 4.67˜4.87(m, 2H),                         material                                                                            7.03(d, 2H, J=9), 7.23(d, 2H,                       __________________________________________________________________________                              J=9)                                            

                                      TABLE 4                                     __________________________________________________________________________    (Cyclopentanone Derivatieves)                                                  ##STR32##                                                                    Compound                                                                            Indication in Formula (IV)                                                                  Physical                                                  No.   R.sup.1                                                                            R.sup.2                                                                           X.sub.n                                                                            property NMR Spectral Data (CDCl.sub.3,                   __________________________________________________________________________                                 δppm)                                      133   CH.sub.3                                                                           CH.sub.3                                                                          4-Cl Oily material                                                                          0.83(s, 3H), 1.05(s, 3H), 1.52˜1.83(m,                                  4H), 2.25˜3.17(m, 3H),                                         BP 124° C.                                                                      6.97(d, 2H, J=8), 7.17(d, 2H, J=8)                                   (1 mmHg)                                                  134   CH.sub.3                                                                           CH.sub.3                                                                          4-Br Oily material                                                                          0.87(s, 3H), 1.07(s, 3H), 1.17˜3.27(m,                                  7H), 6.83˜7.53(m, 4H)                                          BP 131˜2° C.                                                     (0.7 mmHg)                                                135   CH.sub.3                                                                           CH.sub.3                                                                          4-F  Oily material                                                                          0.85(s, 3H), 1.07(s, 3H), 1.20˜3.23(m,                                  7H), 6.73˜7.27(m, 4H)                                          BP 95˜8° C.                                                      (0.7 mmHg)                                                136   CH.sub.3                                                                           CH.sub.3                                                                          2, 4-Cl.sub.2                                                                      Oily material                                                                          0.90(s, 3H), 1.05(s, 3H), 1.3˜2.07(m,                                   4H), 2.23˜3.40(m, 3H),                                         BP 142˜6° C.                                                              7.0˜7.32(m, 3H)                                                (1.5 mmHg)                                                137   CH.sub.3                                                                           H   4-Cl Oily material                                                                          0.97, 1.08(2d, 3H, J=7, J=6),                                                 1.20˜3.27(m, 8H), 7.03(d, 2H, J=7),                            BP 120˜145° C.                                                            7.19(d, 2H, J=7)                                                     (3 mmHg)                                                  138   CH.sub.3                                                                           CH.sub.3                                                                          H    Oily material                                                                          0.87(s, 3H), 1.03(s, 3H), 0.83˜3.23(m,                                  7H), 7.07(s, 5H)                                                     BP 93˜94° C.                                                     (0.3 mmHg)                                                139   CH.sub.3                                                                           CH.sub.3                                                                          4-CH.sub.3                                                                         Oily material                                                                          0.87(s, 3H), 1.07(s, 3H), 1.20˜3.20(m,                                  7H), 2.27(s, 3H), 7.70(s, 4H)                    140   CH.sub.3                                                                           CH.sub.3                                                                          2-F-4-Cl                                                                           Oily material                                                                          0.89(s, 3H), 1.05(s, 3H), 1.32˜3.49(m,                                  7H), 6.83˜7.21(m, 3H)                                          BP 102˜104° C.                                                   (0.3 mmHg)                                                141   CH.sub.3                                                                           CH.sub.3                                                                          4-t-C.sub.4 H.sub.9                                                                Oily material                                                                          0.86(s, 3H), 1.04(s, 3H), 1.26(s, 9H),                                        1.37˜3.21 (m, 7H),                                             BP 132˜140° C.                                                            6.95(d, 2H, J=8.4), 7.18(d, 2H, J=8.4)                               (1.0 mmHg)                                                142   CH.sub.3                                                                           CH.sub.3                                                                          4-C.sub.6 H.sub.5                                                                  Solid    0.87(s, 3H), 1.03(s, 3H), 1.17˜3.40(m,                                  7H), 7.00˜7.67(m, 9H)                                          MP 63˜66° C.                                 143   C.sub.2 H.sub.5                                                                    H   4-Cl Oily material                                                                          0.89(t, 3H, J=7), 1.10˜3.28(m, 10H),                                    7.05(d, 2H, J=9), 7.27(d, 2H, J=9)                                   BP 135˜145° C.                                                   (0.65 mmHg)                                               144   C.sub.2 H.sub.5                                                                    H   4-F  Oily material                                                                          0.70˜1.10(m, 3H), 1.20˜3.28(m,                                    10H), 6.70˜7.25(m, 4H)                                         BP 102˜108° C.                                                   (0.2 mmHg)                                                145   C.sub.2 H.sub.5                                                                    H   4-Br Oily material                                                                          0.87(t, 3H, J=7), 1.10˜3.40(m, 10H),                                    6.97(d, 2H, J=8), 7.32(d, 2H, J=8)                                   BP 126˜128° C.                                                   (0.5 mmHg)                                                146   C.sub.2 H.sub.5                                                                    H   2, 4-Cl.sub.2                                                                      Oily material                                                                          0.90(t, 3H, J=7), 1.10˜3.60(m, 10H),                                    7.13˜7.30(m, 3H)                                               BP 178˜179° C.                                                   (4 mmHg)                                                  147   C.sub.2 H.sub.5                                                                    H   4-t-C.sub.4 H.sub.9                                                                Oily material                                                                          0.87(t, 3H, J=7), 1.00˜3.30(m, 10H),                                    6.87˜7.43(m, 4H)                                               BP 132° C.                                                             (0.5 mmHg)                                                148   C.sub.2 H.sub.5                                                                    H   4-C.sub.6 H.sub.5                                                                  Solid    0.70˜1.07(m, 3H), 1.13˜3.30(m,                                    10H), 6.98˜7.65(m, 9H)                                         MP 72˜75° C.                                 149   n-C.sub.3 H.sub.7                                                                  H   4-Cl Oily material                                                                          0.66˜1.08(m, 3H), 1.08˜3.26(m,                                    12H), 7.04(d, 2H, J=9), 7.24(d, 2H, J=9)                             BP 150˜160° C.                                                   (3 mmHg)                                                  150   i-C.sub.3 H.sub.7                                                                  H   4-Cl Oily material                                                                          0.60˜1.07(m, 6H), 1.07˜3.27(m,                                    9H), 6.83˜7.27(m, 4H)                                          BP 143˜149° C.                                                   (1.2 mmHg)                                                151   n-C.sub.4 H.sub.9                                                                  H   4-Cl Oily material                                                                          0.87(t, 3H, J=7.0), 1.03˜3.28(m, 14H),                                  7.02(d, 2H, J=9.0), 7.25(d, 2H, J=9.0)                               BP 146˜149° C.                                                   (0.6 mmHg)                                                152   n-C.sub.5 H.sub.11                                                                 H   4-Cl Oily material                                                                          0.87(t, 3H, J=7.0), 1.10˜2.50(m, 14H),                                  2.53˜3.10(m, 2H),                                              BP 135˜137° C.                                                            7.08(d, 2H, J=8.3), 7.24(d, 2H, J=8.3)                               (0.06 mmHg)                                               153   C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   4-Cl Oily material                                                                          0.57˜1.07(m, 6H), 1.07˜3.27(m,                                    11H), 6.95˜7.37(m, 4H)                     154   i-C.sub.4 H.sub.9                                                                  H   4-Cl Oily material                                                                          0.85(d, 3H, J=6), 0.90(d, 3H, J=6),                                  BP 130˜136° C.                                                            1.10˜3.33(m, 11H), 7.00(d, 2H, J=9),                                    7.21(d, 2H, J=9)                                                     (0.3 mmHg)                                                155   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   4-Cl Oily material                                                                          0.57˜1.07(m, 6H), 1.17˜3.23(m,                                    9H), 7.00(d, 2H, J=9), 7.20(d, 2H, J=9)                              BP 123˜130° C.                                                   (0.2 mmHg)                                                __________________________________________________________________________

                                      TABLE 5                                     __________________________________________________________________________     ##STR33##                                                                    (Ester Derivatives of Cyclopentanecarboxylic acid)                            Compound                                                                            Indication in Formula (V)                                                                      Physical                                               No.   R.sup.1                                                                            R.sup.2                                                                           X.sub.n                                                                            R  property NMR Spectral Data (CDCl.sub.3, δ                                        ppm)                                          __________________________________________________________________________    156   CH.sub.3                                                                           CH.sub.3                                                                          4-Cl CH.sub.3                                                                         Oily     0.72(s, 3H), 1.05(s, 3H), 1.37˜                                         2.40(m, 4H), 3.13(s, 2H), 3.70(s, 3H),                               material 7.07(d, 2H, J=9), 7.27(d, 2H, J=9)                                   BP 142˜143° C.                                                   (0.7 mmHg)                                             157   CH.sub.3                                                                           CH.sub.3                                                                          4-Br CH.sub.3                                                                         Oily     0.70(s, 3H), 1.03(s, 3H),                                                     1.25˜2.43(m, 4H), 3.07(s, 2H),                                          3.63(s, 3H),                                                         material 6.80˜7.53(m, 4H)                        158   CH.sub.3                                                                           CH.sub.3                                                                          4-F  CH.sub.3                                                                         Oily     0.70(s, 3H), 1.08(s, 3H),                                                     1.20˜2.57(m, 4H), 3.13(s, 2H),                                          3.67(s, 3H),                                                         material 6.73˜7.37(m, 4H)                        159   CH.sub. 3                                                                          CH.sub.3                                                                          2,4-Cl.sub.2                                                                       CH.sub.3                                                                         Oily material                                                                          0.70(s, 3H), 1.05(s, 3H),                                                     1.20˜2.45(m, 4H), 3.10(s, 2H),                                 BP 130˜133° C.                                                            3.65(s, 3H), 7.05˜7.30(m, 3H)                                  (0.60 mmHg)                                            160   CH.sub.3                                                                           H   4-Cl CH.sub.3                                                                         Oily material                                                                          0.83˜1.12(m, 3H),                                                       1.40˜2.63(m, 5H), 3.12, 3.15(2s,                                        2H),                                                                 BP 142˜145° C.                                                            3.70(s, 3H), 7.07(d, 2H, J=8), 7.27(d,                                        2H, J=8)                                                             (0.1 mmHg)                                             161   CH.sub.3                                                                           CH.sub.3                                                                          H    CH.sub.3                                                                         Oily     0.67(s, 3H), 1.03(s, 3H),                                                     0.77˜3.23(m, 4H),                                              material 3.10(s, 2H), 3.63(s, 3H), 7.07(s, 5H)         162   CH.sub.3                                                                           CH.sub.3                                                                          4-CH.sub.3                                                                         CH.sub.3                                                                         Oily     0.70(s, 3H), 1.03(s, 3H),                                                     1.13˜2.40(m, 4H), 2.27(s, 3H),                                          3.07(s, 2H),                                                         material 3.67(s, 3H), 6.97(s, 4H)                      163   CH.sub.3                                                                           CH.sub.3                                                                          2-F-4-Cl                                                                           CH.sub.3                                                                         Oily     0.79(s, 3H), 1.09(s, 3H),                                                     1.18˜2.61(m, 4H), 3.00(d, 1H,                                           J=14),                                                               material 3.33(d, 1H, J=14), 3.70(s, 3H),                                               6.89˜7.32(m, 3H)                        164   CH.sub.3                                                                           CH.sub.3                                                                          4-t-C.sub.4 H.sub.9                                                                CH.sub.3                                                                         Oily     0.68(s, 3H), 1.05(s, 3H), 1.26(s, 9H),                                        1.32˜2.62(m, 4H), 3.10(bs, 2H),                                material 3.68(s, 3H), 7.01(d, 2H, J=8.6), 7.26(d,                                      2H, J=8.6)                                    165   CH.sub.3                                                                           CH.sub.3                                                                          4-C.sub.6 H.sub.5                                                                  CH.sub.3                                                                         Solid    0.75(s, 3H), 1.05(s, 3H),                                                     1.13˜2.88(m, 4H), 3.13(s, 2H),                                          3.62(s, 3H),                                                         mp. 95˜98° C.                                                             6.95˜7.62(m, 9H)                        166   C.sub.2 H.sub.5                                                                    H   4-Cl C.sub.2 H.sub.5                                                                  Oily     0.67˜1.03(m, 3H), 1.20(t, 3H, J=7),                                     1.45˜2.53(m, 9H),                                              material 3.03, 3.08(2s, 2H), 4.10(q, 2H, J=7),                                         6.98(d, 2H, J=9),                                                    BP 152˜160° C.                                                            7.20(d, 2H, J=7)                                                     (0.45 mmHg)                                            167   C.sub.2 H.sub.5                                                                    H   4-F  CH.sub.3                                                                         Oily     0.63˜1.10(m, 3H),                                                       1.21˜2.68(m, 7H), 3.07, 3.11(2s,                                        2H,                                                                  material 3.66(s, 3H), 6.70˜7.22(m, 4H)                                  BP 144˜154° C.                                                   (3.0 mmHg)                                             168   C.sub.2 H.sub.5                                                                    H   4-Br CH.sub.3                                                                         Oily     0.60˜2.90(m, 10H), 3.07, 3.12(2s,                                       2H), 3.67(s, 3H),                                                    material 7.06(d, 2H, J=8.0), 7.42(d, 2H, J=8.0)                               BP 149˜151° C.                                                   (0.5 mmHg)                                             169   C.sub.2 H.sub.5                                                                    H   2,4-Cl.sub.2                                                                       CH.sub.3                                                                         Oily     0.67˜2.82(m, 10H), 3.10(d, 0.4H,                                        J=14), 3.15(d, 0.6H, J=16),                                          material 3.45(d, 0.4H, J=14), 3.50(d, 0.6H, J=14),                                     3.68(s, 3H),                                                         BP 143° C.                                                                      7.08(m, 2H), 7.30(m, 1H)                                             (0.5 mmHg)                                             170   C.sub.2 H.sub.5                                                                    H   4-t-C.sub.4 H.sub.9                                                                CH.sub.3                                                                         Oily     0.72˜2.52(m, 10H), 1.27(s, 9H),                                         3.09(bs, 2H),                                                        material 3.65(s, 3H), 6.79˜7.39(m, 4H)                                  BP 152˜156° C.                                                   (0.2 mmHg)                                             171   C.sub.2 H.sub.5                                                                    H   4-C.sub.6 H.sub.5                                                                  CH.sub.3                                                                         Solid    0.61˜1.10(m, 3H),                                                       1.45˜2.50(m, 7H), 3.11, 3.16(2s,                                        2H), 3.66(s, 3H),                                                    mp. 52˜54° C.                                                             6.96˜7.61(m, 9H)                        172   n-C.sub.3 H.sub.7                                                                  H   4-Cl C.sub.2 H.sub.5                                                                  Oily     0.54˜1.08(m, 3H), 1.22(t, 3H,                                           J=7.4), 1.08˜2.61(m, 9H),                                      material 3.08, 3.13(2s, 2H), 4.15(q, 2H, J=7.4),                                       7.06(d, 2H, J=9.8),                                                           7.27(d, 2H, J=9.8)                            173   n-C.sub.4 H.sub.9                                                                  H   4-Cl CH.sub.3                                                                         Oily     0.85(t, 3H), 0.97˜2.12(m, 11H),                                         3.03, 3.03, 3.08(2s, 2H), 3.62(s, 3H),                               material 6.92(d, 2H, J=8), 7.13(d, 2H, J=8)                                   BP 160˜172° C.                                                   (0.3 mmHg)                                             174   n-C.sub.5 H.sub.11                                                                 H   4-Cl CH.sub.3                                                                         Oily     0.86(t, 3H), 0.98˜2.32(m, 13H),                                         3.05˜3.16(m, 2H),                                              material 3.69, 3.71(2s, 3H), 7.04(d, 2H, J=8.3),                                       7.22(d, 2H, J=8.3)                                                   BP 185˜186° C.                                                   (0.25 mmHg)                                            175   C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   4-Cl CH.sub.3                                                                         Oily     0.50˜2.63(m, 14H), 2.90(d, 1H,                                          J=14), 3.27(d, 1H, J=14),                                            material 3.67(s, 3H), 6.93˜7.37(m, 4H)           176   i-C.sub.3 H.sub.7                                                                  H   4-Cl CH.sub.3                                                                         Oily     0.58˜1.10(m, 6H),                                                       1.10˜3.01(m, 6H),                                              material 3.08, 3.12(2s, 2H), 3.71(s, 3H),                                              6.84˜7.30(m, 4H)                        177   i-C.sub.4 H.sub.9                                                                  H   4-Cl CH.sub.3                                                                         Oily     0.82(d, 3H, J=6), 0.89(d, 3H, J=6),                                  material 1.04˜3.00(m, 8H), 3.07, 3.11(2s,                                        2H), 3.69(s, 3H),                                                             6.77˜7.24(m, 4H)                        178   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   4-Cl CH.sub.3                                                                         Oily     0.58˜1.17(m, 6H),                                                       1.17˜2.87(m, 6H),                                              material 3.05, 3.12(2s, 2H), 3.70(s, 3H),                                     BP 145˜155° C.                                                            7.03(d, 2H, J=9), 7.25(d, 2H, J=9)                                   (0.6 mmHg)                                             __________________________________________________________________________     The NMR spectra of compounds in the Table 1 to 5 are measured by using TM     as internal standard. The notations are as follows.                           s--singlet,                                                                   d--doublet,                                                                   t--triplet,                                                                   q--quartet,                                                                   m--multiplet,                                                                 b--broad line,                                                                j--coupling constant (unit, Hz).                                         

The infrared absorption spectrum of each of the azole derivativesexemplified in Table 1 is shown in each of the attached FIGS. 1 to 76.

In the azole derivative represented by the formula (I), according to theview points of the plant diseases controlling activity and the plantgrowth regulating activity, an azole derivative wherein R¹ is a hydrogenatom or a (C₁ -C₄)alkyl; R² is a hydrogen atom or a (C₁ -C₃)alkyl (bothR¹ and R² do not represent hydrogen atoms at the same time); X is ahalogen atom substituting the 4-position of the benzene ring; n is 1 andA is represented by a nitrogen atom or a CH is preferable, andfurthermore, an azole derivative wherein R¹ and R² respectivelyrepresent a hydrogen atom or a (C₁ -C₃)alkyl group (both R¹ and R² donot represent hydrogen atoms at the same time); X represents a halogenatom substituting the 4-position of the benzene ring; n is representedby 1 and A is represented by a nitrogen atom is particularly preferable.

Of the compounds exemplified in Table 1, those azole derivatives ofCompound Nos. 1-3, 5, 9-11, 16, 18, 29-32, 37, 38, 42-45, 50, 59, 62,63, 65 and 69 are preferable.

The azole derivative according to the present invention is produced bythe following process.

The objective azole derivative represented by the formula (I) can beobtained by reacting the oxirane derivative represented by the formula(II) with a 1,2,4-triazole or imidazole represented by the followingformula (VI) in the presence of a diluent: ##STR34## wherein Mrepresents a hydrogen atom or an alkali metal atom and A represents anitrogen atom or a CH.

The oxirane derivative represented by the formula (II), which is used asthe starting substance can be obtained by the following process.

Namely, by reacting the cyclopentanone represented by the formula (IV)with sulfonium ylide or oxosulfonium ylide, for instance,dimethyloxosulfonium methylide or dimethylsulfonium methylide in thepresence of a diluent while following the methods described in Org. Syn.49, 78 (1968) and in J. Amer. Chem. Soc., (1965) 1353, the oxiranederivative represented by the formula (II) is obtained (this method isreferred to as A-method).

Still more, as a different method (referred to as B-method), there is amethod by which a methylenecyclopentane represented by the formula (III)is obtained from a cyclopentanone represented by the formula (IV)through the Wittig reaction [refer to Org. Syn. 40, 66 (1966) and J.Org. Chem. 28, 1128 (1963)], and then the oxirane derivative representedby the formula (II) can be obtained from the thus prepared compound bythe epoxidation [refer to Org. Syn. Coll. vol., 4, 552 (1963), 49, 62(1969)].

The reaction formulae according to the abovementioned A-method andB-method are shown below. ##STR35##

Still more, the cyclopentanone derivative represented by the formula(IV) can be obtained by the following method:

Namely, in the case where both R¹ and R² of the formula (IV) are thesame (C₁ -C₅)alkyl groups, a cyclopentanone compound represented by theformula (VII) is subjected to dialkylation, thereby converting into theester derivative of cyclopentanecarboxylic acid represented by theformula (V) and the ester derivative represented by the formula (V) issubjected to hydrolysis and decarboxylation, and in the case where anyone of R¹ and R² is a (C₁ -C₅)alkyl group and the other one is ahydrogen atom, a desired benzyl group is introduced into thealkylcyclopentane carboxylate derivative represented by the formula(VIII) to obtain the ester derivative of cyclopentanecarboxylic acidrepresented by the formula (V) and then the thus obtained esterderivative is subjected to hydrolysis and decarboxylation. By doing so,the cyclopentanone derivative represented by the formula (IV) can beobtained.

Further, in the case where R¹ and R² of the formula (IV) are themutually different (C₁ -C₅)alkyl groups, after introducing a different(C₁ -C₅)alkyl group into an ester derivative of cyclopentanecarboxylicacid represented by formula (V) in which either of R¹ or R² is a (C₁-C₅)alkyl group and the other (remainder) is a hydrogen atom, theobtained ester derivative is subjected to hydrolysis anddecarboxylation, thereby obtaining the desired derivative represented bythe formula (IV).

The reaction form of the above-mentioned cyclopentanone is shown below.##STR36##

By the way, the compounds shown in the formulae (VII) and (VIII) areknown and can be obtained from an alkyl ester of2-oxocyclopentanecarboxylic acid by the method described in Org. Syn.45, 7 (1965) and J. Org. Chem. 29, 2781 (1964).

As the diluent used in reactions in the process of producing the azolederivative represented by the formula (I) according to the presentinvention, hydrocarbons such as benzene, toluene, xylene, etc.;halogenohydrocarbons such as methylene chloride, chloroform, carbontetrachloride, etc.; alcohols such as methanol, ethanol, etc.; etherssuch as diethyl ether, diisopropyl ether, tetrahydrofurane, dioxane,etc. and as the others, acetonitrile, acetone, dimethylformamide,dimethylsulfoxide, etc. may be exemplified.

Still more, in the process for producing the azole derivative accordingto the present invention, the reaction is carried out in the coexistenceof a base or an acid in addition to the above-mentioned diluent. As thebase used herein, alkali metal carbonates such as sodium carbonate,potassium carbonate, etc.; alkali metal hydroxides such as sodiumhydroxide, potassium hydroxide, etc.; alkali metal alcoholates such assodium methylate, sodium ethylate, potassium tertiarybutylate, etc.;alkali metal hydrides such as sodium hydride, potassium hydride, etc,;alkyl compounds of an alkali metal such as n-butyl lithium, etc. and asthe others, triethylamine, pyridine may be exemplified.

As the acid, inorganic acids such as hydrochloric acid, hydrobromicacid, hydroiodic acid, sulfuric acid, etc. and organic acids such asformic acid, acetic acid, butyric acid, p-toluenesulfonic acid, etc. maybe exemplified.

In order to enforce the process for production of the azole derivativeaccording to the present invention, for instance, in the case ofobtaining the ester derivative of cyclopentanecarboxylic acidrepresented by the formula (V), it is preferable to react a halogenatedalkyl or a substituted benzyl halide with the compound represented bythe formula (VII) or the formula (VIII) which has been dissolved in thediluent, in the presence of the base as occasion demands. The reactiontemperature may be selected optionally in the range of from thesolidifying temperature of the diluent as the solvent to the boilingpoint thereof, preferably from 0° to 100° C.

The derivative represented by the formula (IV) can be obtained bysubjecting the ester derivative of cyclopentanecarboxylic acidrepresented by the formula (V) to decarboxylation at a temperature offrom 80° to 150° C. with the inorganic acid or organic acid for from 2to 24 hours, preferably under agitation.

In order to produce the oxirane derivative represented by the formula(II), in the case of applying the A-method, it is preferable to add asolution prepared by dissolving a ketone represented by the formula (IV)in the diluent (particularly, dimethylsulfoxide is preferable) todimethyloxosulfonium methylide or dimethylsulfonium methylide preparedby equivalently mixing the base (for instance, sodium hydride) andtrimethyloxosulfonium iodide or trimethylsulfonium iodide, and to reactthe two compounds.

In this case, the reaction amount of dimethyloxosulfonium methylide ordimethylsulfonium methylide is preferably from 1.0 to 2.0 equivalentamount of the cyclopentanone derivative represented by the formula (IV).The reaction is preferably carried out at a temperature in the range offrom 25° to 100° C. for from 1 to 40 hours.

On the other hand, in the case where the production is carried out bythe B-method, the cyclopentanone derivative represented by the formula(IV) is added to triphenylphosphine methylide (Wittig reagent) preparedby equivalently mixing the base (for instance, sodium hydride), andmethyltriphenylphosphonium halide in the diluent (particularly,dimethylsulfoxide is preferable), and to react the two compounds forfrom 2 to 10 hours at a temperature of from 0° to 100° C. The thusformed methylenecyclopentanone derivative represented by the formula(III) is isolated, dissolved in the diluent and reacted at a temperatureof from -10° C. to the boiling point of the diluent, preferably from-10° to 80° C. after adding hydrogen peroxide or an organic per- acidsuch as peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, etc.

The oxirane compound (II) obtained from the cyclopentanone derivativerepresented by the formula (IV) by the A-method or B-method takes thefollowing stereoisomeric structures concerning the conformation of theoxirane group at the 3-position and the substituted benzyl group at the7-position in the 1-oxaspiro[2,4]heptane of the oxirane compoundrepresented by the formula (II): ##STR37##

The separation of these stereoisomers represented by the formulae (II-A)and (II-B) can be carried out by, for instance, chromatography(thin-layer chromatography, column chromatography, high performanceliquid chromatography, etc.). The characteristics of the structure ofthese stereoisomers can be found by, for instance, NMR spectrum.

In order to obtain the azole derivative represented by the formula (I),the oxirane compound represented by the formula (II) is added in thepresence of the base as occasion demands, to a solution prepared bydissolving the azole compound represented by the formula (VI) into thediluent, or conversely, an alkali metal salt of the azole compound isadded to a solution prepared by dissolving the oxirane compound in thediluent, to react the two compounds. The reaction temperature may beselected optionally in the range of from the solidifying point to theboiling point of the diluent, however, practically, it is preferable tocarry out the reaction at a temperature of from 0° to 120° C., morepreferably from 60° to 120° C. for from one to 10 hours under agitation.

After finishing the reaction, the thus obtained reaction mixture iscooled and extracted by an organic solvent such as ethyl acetate,chloroform, methylene chloride, benzene, etc. in a iced water. Afterseparating the organic layer, washing it with water and drying thewashed layer, the solvent is distilled off under a reduced pressure fromthe organic layer. By subjecting the thus obtained residue topurification treatment, the objective compound can be obtained. Thepurification treatment can be carried out by subjecting the residue torecrystallization, silica gel-chromatography, etc.

Because of the existence of the two isomers represented by the formulae(II-A) and (II-B) in the oxirane compound which is the starting compoundof the azole derivative represented by the formula (I), there are thefollowing stereoisomers in the objective azole derivative represented bythe formula (I) which is obtained by the reaction of the oxiranecompound represented by the formula (II) and 1,2,4-triazole or imidazolerepresented by the formula (VI): ##STR38##

Of course, the separation of the isomers represented by the formulae(I-A) and (I-B) can be carried out by, for instance, chromatography.

The utility of the azole derivative (azolylcyclopentanol derivative)represented by the formula (I) according to the present invention as anactive ingredient of the agricultural and horticultural composition willbe explained.

(1) Fungicidal action to plant disease fungi:

The azole derivative according to the present invention shows thecontrolling effect against the following plant diseases in a broadrange.

Pyricularia oryzae on rice plant,

Cochliobolus miyabeanus on rice plant,

Xanthomonas oryzae on rice plant,

Rhizoctonia solani on rice plant,

Helminthosporium sigmoideum on rice plant,

Gibberella fujikuroi on rice plant,

Podosphaera leucotricha on apple,

Venturia inaequalis on apple,

Sclerotinia mali on apple,

Alternaria mali on apple,

Valsa mali on apple,

Alternaria kikuchiana on pear,

Phyllactinia pyri on pear,

Gymnosporangium haraeonum on pear,

Venturia nashicola on pear,

Unccinula necator on grape,

Phakospora ampelopsidis on grape,

Glomerella cingulata on grape,

Erysiphe graminis f. sp. hordei on barley,

Rhynchosporium secalis on barley,

Puccinia graminis on barley,

Puccinia triformis on barley,

Puccinia recondita on wheat,

Septoria tritici on wheat,

Puccinia triformis on wheat,

Erysiphe graminis f. sp. tritici on wheat,

Sphaerotheca fuliginea on melons,

Colletotrichum lagenarium on melons,,

Fusarium oxysporum on watermelon,

Fusarium oxysporum f. cucumerinum on cucumber,

Fusarium oxysporum f. raphani on Japanese radish,

Erysiphe cichoracearum on tomato,

Alternaria solani on tomato

Erysiphe cichoracearum on egg plant,

Sephaerotheca humuli on strawberry,

Erysiphe cichoracearum on tobacco,

Alternaria longipes on tobacco,

Cercospora beticola on sugar beet, .

Alternaria solani on potato,

Septoria glycines on soybean,

Cercospora kikuchii on soybean,

Sclerotinia cinerea on stone fruit trees,

Botrytis cinerea on various crops,

Sclerotinia sclerotiorum, etc.

Furthermore, the azole derivative according to the present inventiontakes not only the prophylactic controlling effect but also thetherapeutic effect on a few diseases among the plant diseases.

(2) Plant growth regulating action:

Accompanying with the elucidation of the mechanism of the plant growthregulation by plant hormones, the chemicals which are called as theplant growth regulating agent have come to be used in the productionfield of agriculture and horticulture in recent years.

For instance, production of seedless grapes by gibberellin, promotion ofrooting of cuttings by α-naphthaleneacetic acid and utilization of2-chloroethyltrimethylammonium chloride (trade name of CCC) as a growthretardant for wheat have been known.

Besides, the application of the regulating technique of the plant lifecircle by using the plant growth regulating agent has been enlarged notonly to crop plants such as cereals, vegetables, fruit trees, etc. butalso to horticultural plants such as flowers, etc. and further to treesas the plants in a broad range, and the function of the plant growthregulating agent has s possibility of cover the promotion of rooting,control of blooming, fruit bearing, enlargement of fruits, growthpromotion, growth control and control of metabolism.

Accordingly, both the kinds and the amount of use of the plant growthregulating agent have shown the increasing tendency in recent years,however, it is the actual state that the practical use of the plantgrowth regulating agent has not been promoted so much as is expected.

The azole derivative (azolylcyclopentanol derivative) according to thepresent invention has a specific property of showing the diverse plantgrowth regulating activity on plants in a broad range, which will beexemplified as follows.

(i) Inhibition of vegetative grow of plants, particularly the growthinhibition of the height of plants,

(ii) Increasing activity of the content of the useful component ofplants, and

(iii) Controlling activity of the ripe timing and the flowering timingof plants.

As the example of utilizing the growth inhibiting activity of (i), thegrowth inhibition of weeds (herbicidal function) and turf; theprevention of falling-down of the easily falling plants such as riceplant, barley, wheat, etc.; the application of the mechanical-yieldmethod of soybean and cotton flower by inhibiting the height thereof;the inhibition of the germination of auxiliary buds for the growthpromotion of the leaves of tobacco; the alleviation of the pruningoperation by the growth inhibition of hedges; the improvement of thecommercial value of the appreciation plants by growth retardationthereof., etc. may be mentioned.

As the example of utilizing the increasing activity of the content ofthe useful component of plants of (ii), the improvement of the qualityof sugar beet, sugar cane and citrus fruits by the increase of sugar;the improvement of the quality of cereals and soybean by the increase ofprotein, etc. may be mentioned, and further, as the example of utilizingthe controlling activity concerning the ripe timing of the fruits andflowering timing of (iii), the appropriation of the shipment of thefresh fruits and live flowers while complying with the demanding season,etc. may be mentioned.

In order to apply the azole derivative represented by the formula (I) asthe fungicide and plant growth regulating agent, the derivative itselfor a mixture of the derivative and a carrier (diluent) is processed intopowders, wettable powders, granules, emulsifiable concentrate, liquidpreparations, etc. and the thus prepared preparations can beadvantageously used.

Still more, it is also possible, of course, to make sure of the effectby adding adjuvants, such as spreaders, emulsifiers, wetting agents,sticking agents other than the carrier as occasion demands.

By the way, since the azole derivative represented by the formula (I)contains a 1,2,4-triazole ring or an imidazole ring, the azolederivative can be used as the form of an acid addition salt with aninorganic acid or organic acid, or as the form of a metal complex.

Still more, since in the azole derivative represented by the formula (I)according to the present invention, an azolylmethyl group, a (C₁-C₅)alkyl group and a substituted benzyl group are respectivelycontained at the 1-position, the 2-position and the 5-position of thecyclopentane ring, the stereoisomers such as geometrical isomers of cisand trans and optical isomers can exist, and the present inventionincludes each of the isomers and the mixtures of each isomer in anoptional ratio.

Accordingly, it is to be recognized that the agricultural andhorticultural composition according to the present invention includesthose containing the single isomer or the mixture of the isomers as theactive ingredient.

The azole derivative represented by the formula (I) according to thepresent invention is excellent the plant diseases controlling activityand the plant growth regulating activity, and is a useful compound asthe active ingredient of the agricultural and horticultural composition.

The effectiveness of the present invention will be explained whileshowing the concrete examples of the agricultural and horticulturalcomposition utilizing the azole derivative according to the presentinvention as the active ingredient, however, the present invention isnot limited to the following examples so far as not coming over theessential features thereof.

[I] The examples of production of the azole derivative represented bythe formula (I) and of each of the intermediates for producing the azolederivative represented by the formula (I).

EXAMPLE 1

Production of methyl1-(4-chlorobenzyl)-3,3-dimethyl-2-oxocyclopentanecarboxylate (theintermediate compound No. 156 shown in Table 5).

Into 150 ml of anhydrous benzene, 5.0 g of sodium hydride (prepared bywashing 60% oily sodium hydride with anhydrous benzene) were added whilestirring under a helium atmosphere, and 50 g of methyl1-(4-chlorobenzyl)-2-oxocylopentanecarboxylate were added to themixture, and the whole mixture was stirred for 40 min at 80° C. Aftercooling the reaction mixture to room temperature, 29.4 g of methyliodide were dropped into the reaction mixture and the thus formedmixture was stirred for 2 hours at 80° C. After cooling the reactionmixture to room temperature, 5.0 g of sodium hydride (one equivalent)were added to the reaction mixture and the reaction mixture was stirredfor 30 min at 80° C. After cooling the reaction mixture again to roomtemperature, 29.4 g of methyl iodide (one equivalent) were added to thereaction mixture and the reaction mixture was stirred for 8 hours at 80°C.

After leaving the thus obtained reaction mixture to cooling, thereaction mixture was poured into a mixture of acetic acid and icedwater, and the whole mixture was extracted by ethyl acetate to obtain anorganic layer. After washing the thus obtained organic layer with anaqueous solution of sodium hydrogen carbonate and then with a salinesolution, the thus washed organic layer was dried on anhydrous sodiumsulfate and the solvent in the organic layer was distilled off under areduced pressure.

By subjecting the thus obtained residue to distillation under a reducedpressure and to purification, 44.8 g of the objective compound [boilingpoint: 142°-143° C. (0.7 mmHg)] were obtained.

EXAMPLE 2

Production of 5-(4-chlorobenzyl)-2,2-dimethyl-1-cyclopentanone(theintermediate compound No. 133 shown in Table 4.

Into 120 ml of 47 % hydrobromic acid, 44.8 g of methyl1-(4-chlorobenzyl)-3,3-dimethyl-2-oxocyclopentanecarboxylate (thecompound No. 156 shown in Table 5) were added, and the thus formedmixture was vigorously stirred for 12 hours at 100° C.

After leaving the thus obtained reaction mixture to cooling, thereaction mixture was poured into iced water and the mixture wasextracted with ethyl acetate to obtain an organic layer. After washingthe organic layer with an aqueous solution of sodium hydrogen carbonateand then with an aqueous saline solution, the organic layer was dried onanhydrous sodium sulfate. By distilling the solvent off from the organiclayer under a reduced pressure, a residue was obtained. By subjectingthe thus obtained residue to distillation under a reduced pressure andto purification, 31 g of the objective compound [boiling point: 124° C.(1 mmHg)] were obtained.

EXAMPLE 3

Production of 5-(4-chlorobenzyl)-2,2-dimethyl-1-methylenecyclopentane(the intermediate compound No. 122 shown in Table 3.

Into 50 ml of anhydrous dimethylsulfoxide, 3.6 g of sodium hydride(prepared by washing 60% oily sodium hydride with-anhydrous benzene)were added under a helium atmosphere, and the thus formed mixture wasstirred for 30 min at 70° C. After cooling the reaction mixture withiced water, 53.6 g of methyltriphenyl phosphonium bromide were added tothe reaction mixture, and the thus formed mixture was stirred for 30 minunder cooling with iced water and then, the thus cooled mixture wasstirred for 10 min at room temperature. Then, 23.6 g of5-(4-chlorobenzyl)-2,2-dimethyl-1-cyclopentanone (the compound No. 133shown in Table 4) were added to the mixture, and the whole mixture wasstirred for one hour at room temperature and then for 30 min at 70° C.to complete the reaction.

After leaving the reaction mixture to cooling, the reaction mixture waspoured into iced water and was extracted with ethyl acetate to obtain anorganic layer. After washing the thus obtained organic layer with anaqueous saline solution, the thus washed organic layer was dried onanhydrous sodium sulfate, and the solvent was distilled off from thethus dried organic layer under a reduced pressure.

From the thus obtained mixture of an oily material and a solid material,the oily material was extracted with n-hexane, and the thus obtainedn-hexane extract was purified by subjecting the extract to silica gelcolumn chromatography to obtain 22.1 g of the objective compound.

EXAMPLE 4

Production of 7-(4-chlorobenzyl)-4,4-dimethyl-1-oxaspiro[2.4]heptane(the intermediate compounds No. 77 and No. 78 shown in Table 2 by theA-method).

Into 70 ml of anhydrous dimethylsulfoxide, 3 g of sodium hydride(prepared by washing 60% oily sodium hydride with anhydrous benzene)were added while stirring dimethylsulfoxide under a helium atmosphere,and then 27.5 g of trimethyloxosulfonium iodide were added to the thusformed mixture. After stirring the whole mixture for 30 min at roomtemperature, a solution of 23.6 g of5-(4-chlorobenzyl)-2,2-di-methyl-1-cyclopentanone (the compound No. 133shown in Table 4) in 20 ml of anhydrous dimethylsulfoxide was addedwithin 30 min to the mixture, and the whole mixture was stirred for 2hours at 90° C.

After leaving the thus obtained reaction mixture to cooling, it waspoured into iced water and the thus obtained mixture was extracted withethyl acetate to obtain an organic layer. After washing the organiclayer with an aqueous saline solution, the layer was dried on anhydroussodium sulfate and the solvent was distilled off from the thus driedorganic layer under a reduced pressure. The thus obtained residue wassubjected to silica gel column chromatography to obtain 13.95 g theobjective compound No. 77 and 1.05 g of the objective compound No. 78.

EXAMPLE 5

Production of 7-(4-fluorobenzyl)-4,4-dimethyl-1-oxaspiro[2.4]heptane(the intermediate compounds No. 81 and No. 82 shown in Table 2 accordingto the B-method).

Into 170 ml of chloroform, 17 g of5-(4-fluorobenzyl)-2,2-dimethyl-1-methylenecyclopentane (the compoundNo. 124 shown in Table 3) were dissolved, and then, 27.1 g ofm-chloroperbenzoic acid were added to the mixture within 10 min, and thethus obtained mixture was stirred for 2 hours at room temperature. Inthe next place, 25.4 g of calcium hydroxide were added to the mixturewithin 10 min, and the mixture was stirred for 30 min at roomtemperature.

After filtering the separated solid material, the chloroform layer ofthe filtrate was condensed to obtain a colourless oily material. Thethus remained oily material was subjected to silica gel columnchromatography to be purified, thereby obtaining 4.5 g of the objectivecompound No. 81 and 8.6 g of the objective compound No. 82.

EXAMPLE 6

Production ofC-5-(2,4-dichlorobenzyl)-2,2-dimethyl-1-(1H-imidazol-1-ylmethyl)-r-1-cyclopentanol(thecompound No. 15 shown in Table 1).

Into 18 ml of anhydrous dimethylformamide, 996 mg of sodium hydride(prepared by washing 60% oily sodium hydride with anhydrous benzene)were added in a helium atmosphere while stirring. In the next place,2.83 g of 1H-imidazole were added to the thus formed mixture and thewhole mixture was stirred at room temperature until the bubblingstopped. To the thus obtained solution, a solution prepared bydissolving 5.93 g of7-[(2,4-dichlorobenzyl)-4,4-dimethyl-1-oxaspiro[2.4]heptane (thecompound No. 83 shown in Table 2) into 10 ml of anhydrousdimethylformamide was dropped, and the thus obtained mixture was stirredfor 2 hours at 80° C.

After leaving the thus obtained reaction mixture to cooling, it waspoured into iced water, and the thus obtained mixture was extracted withethyl acetate to obtain an organic layer.

After washing the organic layer with water, the organic layer was driedwith anhydrous sodium sulfate and the solvent was distilled off from theorganic layer under a reduced pressure.

The thus obtained residue was subjected to purification by silica gelcolumn chromatography, and further to recrystallization with a mixtureof n-hexane and ethyl acetate. As a result, 2.7 g of the objectivecompound were obtained.

EXAMPLE 7

Production oft-5-(4-chlorobenzyl)-2,2-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-r-1-cyclopentanol(the compound No. 2 of Table 1).

Into 30 ml of anhydrous dimethylformamide, 5.0 g of7-(4-chlorobenzyl)-4,4-dimethyl-1-oxaspiro[2.4]heptane (the compound No.78 of Table 2) were added and dissolved while stirring under a heliumatmosphere, and 2.2 g of sodium salt of 1H-1,2,4-triazole (purity: 90%,commercialized, made by Aldrich Co.) were slowly added to the thusformed solution. Then the mixture was stirred for 2 hours at 70° C.

After leaving the thus obtained reaction mixture to cooling, it waspoured into iced water and the whole mixture was extracted with ethylacetate to obtain an organic layer. After washing the organic layer withwater, the organic layer was dried on anhydrous sodium sulfate, and thesolvent was distilled off from the dried organic layer under a reducedpressure.

The thus obtained residue was purified by subjecting the residue tosilica gel column chromatography to obtain 3.1 g of the objectivecompound.

EXAMPLE 8

Production of 2-(4-chlorobenzyl)-5-methyl-1-cyclopentanone (theintermediate compound No. 137 of Table 4).

Into 126 ml of anhydrous benzene, 3.04 g of sodium hydride (prepared bywashing 60% oily sodium hydride with anhydrous benzene) were added, andthen 18 g of methyl 3-methyl-2-oxocyclopentanecarboxylate were added tothe thus formed mixture. After stirring the whole mixture for one hourat room temperature, 21.5 g of 4-chlorobenzyl chloride were added to themixture and the thus obtained mixture was refluxed for 6 hours in an oilbath at 90° C.

After leaving the reaction mixture to cooling, it was extracted withbenzene and the benzene layer was washed with an aqueous salinesolution. After drying the benzene layer on anhydrous sodium sulfate,the solvent was distilled off from the dried benzene layer under areduced pressure to obtained 33.6 g of a yellowish brown oily materialof methyl 1-(4-chlorobenzyl)-3-methyl-2-oxocyclopentanecarboxylate (theintermediate compound No. 160 of Table 5).

Without purifying the thus obtained ester, 100 ml of 47% hydrobromicacid were added to the ester, and the thus formed mixture was vigorouslystirred for 18 hours at 110° C. After leaving the reaction mixture tocooling, it was extracted with methylene chloride and the organic layerwas washed with an aqueous solution of sodium carbonate and then with anaqueous saline solution. The thus washed organic layer was dried onanhydrous sodium sulfate, and the solvent was distilled off from theorganic layer under a reduced pressure.

The thus obtained residue was purified by distillation under a reducedpressure to obtain 17.4 g of the objective compound.

EXAMPLE 9

Production of methyl1-(4-chlorobenzyl)-3-ethyl-3-methyl-2-oxocyclopentanecarboxylate (theintermediate compound No. 178 shown in Table 5).

Into 80 ml of anhydrous tetrahydrofurane, 1.7 g of sodium hydride(prepared by washing 60% oily sodium hydride with anhydrous benzene)were added while stirring under a helium atmosphere, and then, 18.2 g ofmethyl 1-(4-chlorobenzyl)-3-methyl-2-oxocyclopentanecarboxylate [(theintermediate compound No. 160 shown in Table 5) were added to the thusformed mixture and the whole mixture was stirred for 2 hours at a roomtemperature.

In the next place, 11.1 g of ethyl iodide were dropped into the mixturewhile maintaining the mixture at a temperature of from 20° to 30° C.,and then the whole mixture was stirred for one hour at a temperature offrom 20° to 30° C. and successively for one hour at a temperature of 60°C.

After leaving the reaction mixture to cooling, it was poured into amixture of acetic acid and iced water and the whole mixture wasextracted with ethyl acetate to obtain an organic layer. After washingthe organic layer with an aqueous solution of sodium hydrogen carbonatethen, with an aqueous saline solution, the thus washed organic layer wasdried on anhydrous sodium sulfate and the solvent was distilled off fromthe dried organic layer under a reduced pressure.

The thus obtained residue was purified by distillation under a reducedpressure to obtain 15 g of the objective compound.

EXAMPLE 10

Production of 4-(4-chlorobenzyl)-7-methyl-1-oxaspiro[2 4]heptane (theintermediate compound No. 85 in Table 2).

Into 37 ml of anhydrous dimethylsulfoxide, 1.44 g of sodium hydride(prepared by washing 60% oily sodium hydride with anhydrous benzene)were added while stirring under a helium atmosphere, and then 13.2 g oftrimethyloxosulfonium iodide were added to the thus formed mixture andthe whole mixture was stirred for 30 min at room temperature. In thenext place, a solution of 12.2 g of2-(4-chlorobenzyl)-5-methyl-1-cyclopentanone (the compound No. 137 ofTable 4) in 12 ml of anhydrous dimethylsulfoxide was added to themixture within 10 min, and the whole mixture was stirred for 4 hours atroom temperature.

The thus obtained reaction liquid was poured into iced water, and thethus formed mixture was extracted with methylene chloride to obtain anorganic layer. After washing the organic layer with an aqueous salinesolution, the organic layer was dried on anhydrous sodium sulfate, andthe solvent was distilled off from the organic layer under a reducedpressure.

The thus obtained residue was purified by subjecting the residue tosilica gel column chromatography to obtain 6.67 g of the objectivecompound.

Still more, other than the objective compound, three kinds of isomers ofthe objective compound were isolated.

Namely, 0.15 g of the intermediate compound No. 86; 0.16 g of theintermediate compound No. 87 and 0.16 g of the intermediate compound No.88 of Table 2 were obtained.

EXAMPLE 11

Production of 4-(4-chlorobenzyl)-7-ethyl-1-oxaspiro[2 4]heptane [(theintermediate compounds Nos. 93, 94, 95 and 96 in Table 2).

Into 100 ml of chloroform, 8.0 g of2-(4-chlorobenzyl)-5-ethyl-1-methylenecyclopentane (the compound No. 129shown in Table 3) were dissolved, and then 11.6 g of m-chloroperbenzoicacid were added to the thus formed mixture within 5 min, and the wholemixture was stirred for 2 hours at room temperature. In the next place,11 g of calcium hydroxide were added to the mixture under cooling withiced water, and the whole mixture was stirred for 30 min at roomtemperature.

The thus separated solid material was filtered off, and the chloroformlayer of the filtrate was condensed to obtain a colourless oilymaterial. The oily material was purified by subjecting it to silica gelcolumn chromatography to obtain 0.7 g of the compound No. 93; 2.4 g ofthe compound No. 94; 2.2 g of the compound No. 95 and 2.6 g of thecompound No. 96 of the entitled compound.

EXAMPLE 12

Production ofC-2-(4-chlorobenzyl)-5-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)-r-1-cyclopentanol(the compound No. 16 of Table 1).

Into 10 ml of anhydrous dimethylformamide, 630 mg of sodium hydride(prepared by washing 60% oily sodium hydride with anhydrous benzene)were added and then, 1.8 g of 1H-1,2,4-triazole were added to themixture and the whole mixture was stirred at room temperature until thebubbling was settled.

Into the thus obtained reaction mixture, a solution of 3.1 g of4-(4-chlorobenzyl)-7-methyl-1-oxaspiro[2.4]heptane (the compound No. 85in Table 2) in 6.2 ml of anhydrous dimethylformamide was added, and thethus formed mixture was stirred for one hour at 80° C.

After leaving the thus obtained reaction liquid to cooling, it waspoured into iced water, and the thus obtained mixture was extracted withmethylene chloride to obtain an organic layer.

After washing the organic layer with an aqueous saline solution, theorganic layer was dried on anhydrous sodium sulfate and the solvent wasdistilled off from the organic layer under a reduced pressure.

The thus obtained residue was purified by subjecting the residue tosilica gel column chromatography, and was further recrystallized from amixture of n-hexane and ethyl acetate to obtain 2.83 g of the objectivecompound.

EXAMPLE 13

Production ofC-2(4-chlorobenzyl)-5-methyl-1-(1H-imidazol-1-ylmethyl)-r-1-cyclopentanol(the compound No. 17 of Table 1).

Into 10 ml of anhydrous dimethylformamide, 670 mg of sodium hydride(prepared by washing 60% oily sodium hydride) were added and then, 1.9 gof 1H-imidazole were added to the thus formed mixture and the wholemixture was stirred at room temperature until the bubbling was settled.

In the next place, a solution of 3.3 g of4-(4-chlorobenzyl)-7-methyl-1-oxaspiro[2.4]heptane (the compound No. 85of Table 2) in 6.6 ml of anhydrous dimethylformamide was added to themixture, and the whole mixture was stirred for one hour at 80° C.

After leaving the thus obtained reaction liquid to cooling, it waspoured into iced water and the thus formed mixture was extracted withmethylene chloride to obtain an organic layer.

After washing the organic layer with an aqueous saline solution, theorganic layer was dried on anhydrous sodium sulfate and the solvent wasdistilled off from the organic layer under a reduced pressure.

The thus obtained residue was purified by subjecting the residue tosilica gel column chromatography and was further recrystallized from amixture of n-hexane and ethyl acetate to obtain 3.16 g of the objectivecompound.

[II] The examples of preparing the agricultural and

horticultural fungicide compositions.

EXAMPLE 14 Dust (powder)

Three parts by weight of the azole derivative according to the presentinvention (the compound No. 3), 40 parts by weight of clay and 57 partsby weight of talc were mixture and pulverized to prepare an agriculturaland horticultural fungicide composition of dust form.

The thus prepared composition is used by scattering.

EXAMPLE 15 Wettable powder

Fifty parts by weight of the azole derivative according to the presentinvention (the compound No. 1), 5 parts by weight of a salt ofligninsulfonic acid, 3 parts by weight of a salt of alkylsulfonic acidand 42 parts by weight of diatomaceous earth were mixed and pulverizedto prepare a wettable powder.

The thus prepared composition was used as a wettable powder afterdiluting with water.

EXAMPLE 16 Granule

Five parts by weight of the azole derivative according to the presentinvention (the compound No. 16), 43 parts by weight of bentonite, 45parts by weight of clay and 7 parts by weight of a salt ofligninsulfonic acid were uniformly mixed, and after adding water to themixture, the whole materials were kneaded together, processed intogranular form by an extruding granulator and dried to obtain thecomposition of granular form.

EXAMPLE 17 Emulsifiable concentrate

Twenty parts by weight of the azole derivative according to the presentinvention (the compound No. 13), 10 parts by weight of a polyoxyethylenealkyl aryl ether, 3 parts by weight of a polyoxyethylene sorbitanmonolaurate and 67 parts by weight of xylene were uniformly mixedtogether to prepare the composition of emulsifiable concentrate form.

[III] The examples of application of the agricultural and horticulturalfungicide composition according to the present invention to plantdiseases.

EXAMPLE 18

Test for controlling effect against Erysiphe graminis f. sp. tritici onwheat

Onto the young seedlings of wheat of the second leaf stage (variety:NORIN No. 64, 16 seedlings per pot and 3 pots being used in the treatedplot), which had been cultured while using unglazed pots of 10 cm indiameter, 5 ml per pot of an aqueous suspension of the wettable powderprepared in Example 15 (diluted with water to a predeterminedconcentration) were applied. After air drying the applied dilution, asuspension of the summer spores of Erysiphe graminis f. sp. tritici,which had been collected from the attacked leaf of wheat was sprayedonto the seedlings in the pots, the pots were maintained at from 20° to24° C. for 24 hours under a highly humid condition and then the potswere left in a glass room. On the day after 9 to 11 days of theinoculation, the extent of the disease on the seedlings was investigatedaccording to the following investigation standards and the control valueof the fungicide composition was calculated according to the followingformula.

    ______________________________________                                        (Investigation standards)                                                     Degree of disease                                                                             Extent of disease                                             ______________________________________                                        0               not attacked                                                  0.5             The rate of area of the disease                                               spots is below 10%                                            1               The rate of area of the disease                                               spots is not less than 10% and                                                below 20%                                                     2               The rate of area of the disease                                               spots is not less than 20% and                                                below 40%                                                     3               The rate of area of the disease                                               spots is not less than 40% and                                                below 60%                                                     4               The rate of area of the disease                                               spots is not less than 60% and                                                below 80%                                                     5               The rate of area of the disease                                               spots is not less than 80%.                                   ______________________________________                                         ##STR39##                                                                    ?  The results of the test are shown in Table 6.                          

                  TABLE 6                                                         ______________________________________                                        Compound tested                                                                            Concentration of spray                                                                        Control value                                    (No. in Table 1)                                                                           (ppm)           (%)                                              ______________________________________                                        1            125             100                                              2            125             100                                              3            125              95                                              4            125             100                                              5            125             100                                              6            125             100                                              7            125              95                                              8            125              95                                              9            125             100                                              10           125             100                                              11           125             100                                              12           125              90                                              13           125             100                                              14           125             100                                              15           125              95                                              16           125             100                                              17           125              95                                              18           125             100                                              19           125             100                                              20           125              50                                              21           125             100                                              22           125             100                                              23           125             100                                              24           125             100                                              25           125             100                                              26           125             100                                              27           125             100                                              28           125             100                                              29           125             100                                              30           125             100                                              31           125             100                                              32           125             100                                              33           125             100                                              34           125             100                                              35           125             100                                              36           125             100                                              37           125             100                                              38           125             100                                              39           125             100                                              40           125             100                                              41           125             100                                              42           125             100                                              43           125              95                                              44           125             100                                              45           125             100                                              46           125              95                                              47           125             100                                              48           125             100                                              49           125             100                                              50           125             100                                              51           125             100                                              52           125             100                                              53           125              75                                              54           125             100                                              55           125             100                                              56           125             100                                              57           125             100                                              58           125             100                                              59           125             100                                              60           125             100                                              61           125             100                                              62           125             100                                              63           125             100                                              64           125             100                                              65           125             100                                              66           125             100                                              67           125             100                                              68           125             100                                              69           125             100                                              70           125             100                                              71           125             100                                              72           125             100                                              73           125             100                                              74           125             100                                              75           125             100                                              76           125             100                                              Commerciallized                                                                            125             100                                              material                                                                      Triadimephon*                                                                 Control (not treated)         0                                               ______________________________________                                         (Note)                                                                        Triadimephon of the commerciallized material has the compound represented     by the following formula as the active ingredient.                            ##STR40##                                                                

EXAMPLE 19

Test for controlling effect against Sphaerotheca fuliginea on cucumber.

Onto the cucumber plants of the second-leaf stage (variety: SAGAMIHAMPAKU, one plant per pot and 3 pots being used in the treated plot),which had been cultured while using unglazed pots of 10 cm in diameter,5 ml per pot of an aqueous suspension o; f the wettable powder preparedin Example 15 (diluted with water to a predetermined concentration) wereapplied. After air-drying the applied leaves, the spores of Sphaerothecafuliginea were sprinkled with a brush from the diseased leaf of cucumberto inoculate the cucumber plants and the disease was caused on theplants in a glass room.

On the day after from 9 to 11 days of the inoculation, the degree ofdisease on the cucumber plants was investigated according to thefollowing investigation standards and the control value of the fungicidecomposition was calculated according to the following formula:

    ______________________________________                                        (Investigation standards)                                                     Degree of disease                                                                             Extent of disease                                             ______________________________________                                        0               not attacked                                                  0.5             The rate of area of the disease                                               spots is below 10%                                            1               The rate of area of the disease                                               spots is not less than 10% and                                                below 20%                                                     2               The rate of area of the disease                                               spots is not less than 20% and                                                below 40%                                                     3               The rate of area of the disease                                               spots is not less than 40% and                                                below 60%                                                     4               The rate of area of the disease                                               spots is not less than 60% and                                                below 80%                                                     5               The rate of area of the disease                                               spots is not less than 80%                                    ______________________________________                                         ##STR41##                                                                    ?   The results are shown in Table 7.                                     

                  TABLE 7                                                         ______________________________________                                                         Concentration Control                                        Compound tested  of spray      value                                          (No. in Table 1) (ppm)         (%)                                            ______________________________________                                         1               125           100                                             2               125           100                                             3               125           100                                             4               125           100                                             5               125           100                                             6               125           100                                             7               125           100                                             8               125           100                                             9               125           100                                            10               125           100                                            11               125           100                                            12               125           100                                            13               125           100                                            14               125           100                                            15               125           100                                            16               125           100                                            17               125           100                                            Commerciallized material                                                                       125           100                                            Triadimephon*                                                                 Control (not treated)           0                                             ______________________________________                                    

EXAMPLE 20

Test for controlling effect against Puccinia recondita on wheat.

Onto the young seedlings of wheat of the second-leaf stage (variety:NORIN No. 64, 16 seedlings per pot and 3 pots being used in the treatedplot), which had been cultured while using unglazed pots of 10 cm indiameter, 5 ml per pot of an aqueous suspension of the wettable powderprepared in Example 15 (diluted with water to a predeterminedconcentration) were applied by spraying.

After air-drying the applied dilution, a suspension of the summer sporesof Puccinia recondita, which had been collected from the contracted leafof wheat, was sprayed onto the seedlings in the pots, the pots weremaintained at from 20° to 23° C. for 24 hours under a highly humidcondition and then the pots were left in a glass room. On the day after7 to 10 days of the inoculation, the extent of the disease on tenseedlings was investigated according to the following investigationstandards and the control value of the fungicide composition wascalculated according to the following formula from the mean degree ofdisease per leaf.

    ______________________________________                                        (Investigation standards)                                                     Degree of disease                                                                             Extent of disease                                             ______________________________________                                        0               not attacked                                                  0.5             The rate of area of the disease                                               spots is below 10%                                            1               The rate of area of the disease                                               spots is not less than 10% and                                                below 20%                                                     2               The rate of area of the disease                                               spots is not less than 20% and                                                below 40%                                                     3               The rate of area of the disease                                               spots is not less than 40% and                                                below 60%                                                     4               The rate of area of the disease                                               spots is not less than 60% and                                                below 80%                                                     5               The rate of area of the disease                                               spots is not less than 80%.                                   ______________________________________                                         ##STR42##                                                                

The results are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                                        Concentration                                                 Compound tested of spray     Control value                                    (No. in Table 1)                                                                              (ppm)        (%)                                              ______________________________________                                         1              125          100                                               2              125           95                                               3              125          100                                               4              125           95                                               5              125          100                                               6              125          100                                               7              125          100                                               8              125           95                                               9              125          100                                              10              125          100                                              11              125          100                                              12              125           95                                              13              125          100                                              14              125          100                                              15              125          100                                              16              125          100                                              17              125           95                                              18              125          100                                              19              125          100                                              21              125          100                                              22              125          100                                              23              125          100                                              24              125           70                                              25              125          100                                              26              125           95                                              27              125          100                                              28              125          100                                              29              125          100                                              30              125          100                                              31              125          100                                              32              125          100                                              33              125          100                                              34              125          100                                              35              125          100                                              36              125          100                                              37              125          100                                              38              125          100                                              39              125          100                                              40              125          100                                              41              125          100                                              42              125          100                                              43              125          100                                              44              125          100                                              45              125          100                                              46              125          100                                              47              125          100                                              48              125          100                                              49              125           90                                              50              125          100                                              51              125          100                                              52              125          100                                              53              125           95                                              54              125          100                                              55              125          100                                              56              125          100                                              57              125          100                                              58              125           90                                              59              125          100                                              60              125           90                                              61              125           90                                              62              125          100                                              63              125          100                                              64              125          100                                              65              125          100                                              66              125          100                                              67              125          100                                              68              125          100                                              69              125          100                                              70              125          100                                              71              125          100                                              72              125          100                                              73              125          100                                              74              125          100                                              75              125           90                                              76              125           90                                              Commerciallized material                                                                      125           95                                              Triadimephon*                                                                 Control (not treated)         0                                               ______________________________________                                    

EXAMPLE 21

Test for controlling effect against Botrytis cinerea on kidney bean.

Onto the leaves of kidney bean plants at the first true-leaf stage(variety: HONKINTOKI), which had been cultured while using unglazed potsof 10 cm in diameter, 5 ml per pot of an aqueous suspension of thewettable powder prepared in Example 15 (diluted with water to apredetermined concentration) were applied by spraying.

After air-drying the thus applied leaves, a circular cutting of agar ofa diameter of 4 mm containing the fungi of Botrytis cinerea, which hadbeen preliminarily cultured for 3 days at 20° C. while using asugar-added agar medium containing potato soup, was directly adhered tothe center part of the leaf of kidney bean plants, and the plants weremaintained at a temperature of from 20° to 22° C. under a highly humidcondition. On the 3rd day of the inoculation, the area of disease spotof the thus treated plot was compared with that of the control(untreated) plot to investigate the degree of disease according to thefollowing investigation standards and the control value of the fungicidecomposition was calculated according to the following formula.

    ______________________________________                                        (Investigation standards)                                                     Degree of disease                                                                            Extent of disease                                              ______________________________________                                        0              not attacked                                                   0.5            Only attacked the part just below                                             the inoculated fungi-containing                                               agar and the peripheral parts                                                 thereof.                                                       1              The rate of area of the disease                                               spots is below 20%                                             2              The rate of area of the disease                                               spots is not less than 20% and                                                below 40%                                                      3              The rate of area of the disease                                               spots is not less than 40% and                                                below 60%                                                      4              The rate of area of the disease                                               spots is not less than 60% and                                                below 80%                                                      5              The rate of area of the disease                                               spots is not less than 80%.                                    ______________________________________                                         ##STR43##                                                                

The results are shown in Table 9.

                  TABLE 9                                                         ______________________________________                                        Compound tested                                                                            Concentration of spray                                                                        Control value                                    (No. in Table 1)                                                                           (ppm)           (%)                                              ______________________________________                                        1            500             100                                              2            500             100                                              3            500              90                                              4            500              80                                              5            500             100                                              6            500             100                                              7            500              70                                              8            500              70                                              9            500             100                                              10           500             100                                              11           500              85                                              12           500              80                                              13           500             100                                              14           500             100                                              15           500              90                                              16           500             100                                              17           500              80                                              18           500             100                                              19           500             100                                              21           500             100                                              22           500              65                                              23           500             100                                              24           500              90                                              25           500              85                                              27           500             100                                              28           500              90                                              29           500             100                                              30           500             100                                              31           500              60                                              32           500             100                                              33           500              85                                              37           500             100                                              38           500             100                                              39           500              75                                              41           500             100                                              42           500             100                                              44           500             100                                              45           500             100                                              46           500              70                                              47           500              60                                              48           500             100                                              49           500             100                                              50           500             100                                              54           500             100                                              55           500             100                                              56           500              95                                              57           500              70                                              58           500              70                                              59           500              80                                              60           500              80                                              61           500              85                                              62           500             100                                              63           500             100                                              64           500              80                                              65           500             100                                              66           500              60                                              67           500             100                                              68           500              60                                              69           500             100                                              70           500              65                                              71           500             100                                              72           500             100                                              73           500              80                                              74           500              60                                              75           500              85                                              76           500              60                                              Commerciallized                                                                            500             100                                              material                                                                      Rovral*                                                                       ______________________________________                                         (Note)                                                                        *The commerciallized material (Rovral) contains the compound represented      by the following formula as an active ingredient.                             ##STR44##                                                                

EXAMPLE 22

Test for controlling effect against Cochliobolus miyabeanus on riceplant.

In each of unglazed pots of 10 cm in diameter, 16 seeds of rice plate(variety: SASANISHIKI) were sown, and at the time when the riceseedlings became the 4-5 leaf-stage, an aqueous suspension of thewettable powder prepared in Example 15 (diluted to a predeterminedconcentration with water) was sprinkled onto the seedlings.

After air-drying the thus treated leaves, 5 ml per pot of a suspensionof the spores of Cochliobolus mivabeanus, which had been preliminarilycultured, were applied by spraying to the thus treated seedlings. Underthe microscope of 150 magnifications, 15 spores of the fungus in thesuspension were found in the field.

Just after finishing the inoculation, the thus treated pots wereintroduced into an inoculation room at 25° C. and at a saturatedhumidity and after keeping the pots therein for 2 days, the pots wereintroduced into a glass house to be attacked. On the 5th day of theinoculation, the number of disease spots on 10 leaves per pot wascounted, and the control value of the fungicidal composition wascalculated according to the following formula: ##EQU1## The results areshown in Table 10.

                  TABLE 10                                                        ______________________________________                                                           Concentration                                                                             Control                                        Compound tested    of spray    value                                          (No. in Table 1)   (ppm)       (%)                                            ______________________________________                                         1                 125         100                                             2                 125         100                                             3                 125         100                                             4                 125         100                                             5                 125         100                                             6                 125         100                                             7                 125         100                                             8                 125         100                                             9                 125         100                                            10                 125         100                                            11                 125         100                                            12                 125         100                                            13                 125         100                                            14                 125          95                                            15                 125          90                                            16                 125         100                                            17                 125         100                                            Commerciallized material: Rovral                                                                 125          85                                            Control (not treated)           0                                             ______________________________________                                    

EXAMPLE 23

Antifungal test against several pathogenic fungi.

The present example shows the results of the antifungal property of theazole derivative according to the present invention against variousplant-pathogenic fungi.

Test method

The compound according to the present invention is dissolved intodimethyl sulfoxide so as to give a solution of the predeterminedconcentration and 0.6 ml of the thus prepared solution is well mixedwith 60 ml of the PAS culture medium of about 60° C. in a conical flaskof 100 ml in capacity. The thus formed mixture is poured into a glassdish and is solidified to be a flat culture medium containing thecompound.

On the other hand, the test fungus, which has been preliminarilycultured in a flat culture medium, is striked by a cork borer of 4 mm indiameter and the thus striked piece of the culture medium containing thetest fungus is inoculated on the flat culture medium containing thecompound. After inoculation, the thus prepared culture medium containingthe compound and the fungus is cultured for from 1 to 3 days at anappropeiate temperature for growing each of the fungi, and the growth ofthe fungus is measured by the diameter of the fungal colony. Bycomparing the growth of the fungus in the thus prepared culture mediumwith that in the untreated plot (the culture medium not containing thecompound), the rate of inhibiting the mycelial growth of the fungus isobtained according to the following formula.

    R=(dc-dt) 100/dc

wherein R is the rate of inhibiting the mycelial growth; dc is thediameter of fungal colony on the flat medium not containing the compoundand dt is the diameter of fungal colony on the flat medium containingthe compound

The results are evaluated into 5 stages according to the followingstandards and shown in Table 11. Rate of inhibiting the mycelial growth:

5: The rate of inhibiting the growth is not smaller than 90-100%

4: The rate of inhibiting the growth is not smaller than 70% and below90%

3: The rate of inhibiting the growth is not smaller than 40% and below70%

2: The rate of inhibiting the growth is not smaller than 20% and below40%

1: The rate of inhibiting the growth is below 20%

                                      TABLE 11                                    __________________________________________________________________________    No. of                                                                              Concen-                                                                 compound                                                                            tration of                                                              tested (No.                                                                         Compound                                                                            Fungus Tested                                                     in Table 1)                                                                         (μg/ml)                                                                          P.o.                                                                             C.m.                                                                             G.f.                                                                             H.s.                                                                             R.s.                                                                             Bo.c.                                                                            S.s.                                                                             F.n.                                                                             F.c.                                                                             F.r.                                                                             C.l.                                                                             C.b.                                                                             S.c.                                                                             V.m.                                                                             A.k.                                                                             A.m.                                                                             G.c.              __________________________________________________________________________     1    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                  2    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                  3    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                  4    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                  5    100   5  5  5  5  5  5  5  5  5  5  5  5  5  4  5  5  5                  6    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                  7    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                  8    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                  9    100   5  5  5  5  4  5  5  5  5  5  5  5  5  5  5  4  5                 10    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 11    100   5  5  5  5  4  5  5  5  5  5  5  5  5  5  5  5  5                 12    100   5  5  5  5  4  5  5  5  5  5  5  5  5  5  5  5  5                 13    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  4  4  5                 14    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  4  4  5                 15    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 16    100   5  5  5  5  4  5  5  5  5  5  5  5  5  5  5  5  5                 17    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 18    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 19    100   5  5  5  4  4  5  4  5  5  5  5  5  5  5  4  4  5                 20    100   5  5  5  5  4  5  5  5  5  5  5  5  5  5  5  5  5                 21    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 22    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 23    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 24    100   5  5  5  5  4  5  5  5  5  5  5  5  5  5  5  5  5                 25    100   5  5  5  5  5  5  5  5  5  5  5  4  5  5  5  5  5                 26    100   5  5  5  5  4  5  5  5  5  5  5  5  5  5  5  5  5                 27    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 28    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 29    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 30    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 31    100   5  5  5  5  4  5  5  5  5  5  5  5  5  5  4  4  5                 32    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 33    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 34    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 35    100   5  5  5  5  5  5  5  5  5  5  5  3  5  5  5  5  5                 36    100   5  5  5  5  5  5  5  5  5  5  5  3  5  5  5  5  5                 37    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 38    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 39    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 40    100   5  5  4  5  5  5  4  4  4  4  5  3  5  5  4  5  5                 41    100   5  5  5  5  5  5  5  5  5  5  5  3  5  5  5  5  5                 42    100   5  5  5  5  3  5  5  5  5  5  5  5  5  5  5  5  5                 43    100   5  5  5  5  4  5  5  5  5  5  5  5  5  5  5  5  5                 44    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 45    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 46    100   5  4  5  5  3  5  5  4  4  4  5  5  5  5  4  4  5                 47    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  4  5                 48    100   5  5  4  5  5  4  4  4  4  4  5  5  5  5  4  5  5                 49    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 50    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 51    100   5  4  5  5  4  5  5  4  4  4  5  4  5  5  4  4  5                 52    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 53    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 54    100   5  5  5  5  4  5  5  5  5  5  5  4  5  5  4  4  5                 55    100   5  4  5  5  5  5  5  5  5  5  5  4  5  5  4  4  5                 56    100   5  4  5  5  4  5  5  4  4  4  5  3  5  5  3  3  5                 57    100   5  4  5  5  4  5  5  5  5  5  5  4  5  5  4  4  5                 58    100   5  4  5  5  5  5  5  5  5  5  5  3  5  5  3  3  5                 59    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 60    100   5  5  5  5  5  5  5  5  5  5  5  4  5  5  5  4  5                 61    100   5  5  5  5  5  5  5  5  5  5  5  4  5  5  5  4  5                 62    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 63    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 64    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 65    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 66    100   5  5  5  5  3  5  5  5  5  5  5  5  5  5  5  5  5                 67    100   5  5  5  5  4  5  5  5  5  5  5  5  5  5  5  5  5                 68    100   5  5  5  5  3  5  5  4  4  4  5  5  5  5  4  4  5                 69    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 70    100   5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5  5                 71    100   5  5  5  5  4  5  5  5  5  5  5  5  5  5  5  5  5                 75    100   5  5  5  5  5  5  5  5  5  5  5  4  5  5  5  4  5                 76    100   5  5  5  5  5  5  5  5  5  5  5  4  5  5  5  4  5                 __________________________________________________________________________

The abbreviation in Table 11 shows each of the following fungi:

P.o.: Pyricularia oryzae on rice plant

C.m.: Cochliobolus miyabeanus on rice plant

G.f.: Gibberella fujikuroi on rice plant

H.s.: Helminthosporium siomoideum on rice plant

R.s.: Rhizoctonia solani on rice plant

Bo.c.: Botrytis cinerea

S.s.: Sclerotinia sclerotirum

F.n.: Fusarium oxysporum f. niveum on water melon

F.c.: Fusarium oxysporum f. cucumerinum on cucumber

F.r.: Fusarium oxysporum f. raphani on Japanese radish

C.l.: Colletotrichum lagenarium on melons

C.b.: Cercospola beticola on sugar beet

S.c.: Sclerotinia cinerea on peach

V.m.: Valsa mali on apple

A.m.: Alternaria mali on apple

A.k.: Alternaria alternata (kikuchiana) on pear

G.c.: Glomerella cingulata on grape [IV] The examples of theagricultural and horticultural plant growth regulating agent containingthe azole derivative according to the present invention as an activeingredient.

EXAMPLE 24 Form of wettable powder

Fifty parts by weight of the azole derivative according to the presentinvention (the compound No. 3 in Table 1), 5 parts by weight of a saltof ligninsulfonic acid, 3 parts by weight of a salt of alkylsulfonicacid and 42 parts by weight of diatomaceous earth were mixed andpulverized to obtain a composition of the form of wettable powder. Thecomposition is used after diluting with water.

EXAMPLE 25 Form of emulsifiable concentrate

Twenty five parts by weight of the azole derivative according to thepresent invention (the compound No. 20 in Table 1), 65 parts by weightof xylene and 10 parts by weight of polyoxyethylene alkyl aryl etherwere uniformly mixed together to obtain a composition of the form ofemulsifiable concentrate. The composition is used after diluting withwater.

EXAMPLE 26 Form of dust(powder)

Eight parts by weight of the azole derivative according to the presentinvention (the compound No. 11 in Table 1), 40 parts by weight ofbentonite, 45 parts by weight of clay and 7 parts by weight of a salt ofligninsulfonic acid were mixed uniformly, and after adding water to thethus formed mixture, the whole mixture was kneaded together andprocessed into granular form by an extruding granulator and the granularmaterial was dried to be the composition of the form of dust.

EXAMPLE 27 Plant height-restraining effect on rice plant

Into each of the glass dishes of 8.5 cm in diameter, 10 ml of a solutioncontaining each of the compounds according to the present invention at aconcentration of 10 ppm were introduced, and 10 seed of rice plant(variety: SASANISHIKI) were sown in the glass dish. The dishes were keptin a room at 27° C. for 7 days to germinate the seeds, and then theheight of the seedlings were measured to obtain the data shown in Table12.

As are seen in Table 12, every one of the tested azole derivativesaccording to the present invention showed the growth-restraining effectwithout giving any phytotoxicity.

                  TABLE 12                                                        ______________________________________                                                        Rate of                                                                       restraining                                                   No. of compound the height                                                    (No. in Table 1)                                                                              (%)       Phytotoxicity                                       ______________________________________                                         1              84.2      none                                                 2              63.8      none                                                 3              71.8      none                                                 4              70.0      none                                                 5              70.0      none                                                 6              74.6      none                                                 7              85.9      none                                                 8              72.3      none                                                 9              75.7      none                                                10              79.7      none                                                11              76.8      none                                                12              67.2      none                                                13              87.0      none                                                14              76.8      none                                                15              77.4      none                                                16              84.2      none                                                17              76.8      none                                                ______________________________________                                    

What is claimed is:
 1. An azole compound represented by the formula (I):##STR45## wherein R¹ and R² respectively represent a C₁ -C₅ alkyl groupor a hydrogen atom; X represents a halogen atom, a C₁ -C₅ alkyl group ora phenyl group; n represents an integer from 0 to 2 and A represents anitrogen atom, provided that R¹ is not a hydrogen atom when R² is ahydrogen atom.
 2. The azole compound according to claim 1, wherein R¹ isa hydrogen atom or a C₁ -C₄ alkyl group; R² is a hydrogen atom or a C₁-C₃ alkyl group; X is a halogen atom at the 4-position of the benzenering; n is 1 and A is a nitrogen atom, provided that R¹ is not ahydrogen atom when R² is a hydrogen atom.
 3. The azole compoundaccording to claim 2, wherein R¹ and R² respectively represent ahydrogen atom or a C₁ -C₃ alkyl group and A is a nitrogen atom, providedthat R¹ is not a hydrogen atom when R² is a hydrogen atom.
 4. Anagricultural and horticultural composition having fungicidal and plantgrowth regulating activities, which comprises a fungicidal and plantgrowth regulating effective amount of an azole compound, as an activeingredient, represented by the formula (I): ##STR46## wherein R¹ and R²respectively represent a C₁ -C₅ alkyl group or a hydrogen atom; Xrepresents a halogen atom, a C₁ -C₅ alkyl group or a phenyl group; nrepresents an integer of from 0 to 2, and A represents a nitrogen atom,provided that R¹ is not a hydrogen atom when R² is a hydrogen atomtogether with a suitable carrier or diluent.
 5. The agricultural andhorticultural composition according to claim 4, wherein R¹ is a hydrogenatom or a C₁ -C₄ alkyl group; R² is a hydrogen atom or a C₁ -C₃ alkylgroup; X is a halogen atom at the 4-position of the benzene ring; n is 1and A is represented by a nitrogen atom, provided that R¹ is not ahydrogen atom when R² is a hydrogen atom.
 6. The agricultural andhorticultural composition according to claim 5, wherein R¹ and R²respectively represent a hydrogen atom or a C₁ -C₃ alkyl group and A isa nitrogen atom, provided that R¹ is not a hydrogen atom when R² is ahydrogen atom.